Double attachment reactive dyes having alkyl- or alkenylsulfonyl and alkyl- or alkenylsulfonylalkyl groups

ABSTRACT

Double attachment reactive dyes have the formula ##STR1## where U 1  is C 1  -C 4  -alkyl, phenyl, C 2  -C 10  -alkenyl or the radical ##STR2## where Q 1  and Q 2  are each independently of the other hydrogen or C 1  -C 4  -alkyl and Q 3  is a group which is detachable under alkaline reaction conditions, 
     Z is the radical ##STR3##  where each Q 4  is independently of the other hydrogen or C 1  -C 4  -alkyl which may be substituted by cyano, U 2  is C 1  -C 4  -alkyl, phenyl, C 2  -C 10  -alkenyl or the radical ##STR4## where Q 5  and Q 6  are each independently of the other hydrogen or C 1  -C 4  -alkyl and Q 7  is a group which is detachable under alkaline reaction conditions, and w is 0, 1 or 2, 
     t is 0, 1 or 2, 
     v is 1 or 2 and X and L are each as defined in the description, with the proviso that at least one of the two radicals U 1  and U 2  is not C 1  -C 4  -alkyl or phenyl, and are prepared from benzyl compounds of the formula ##STR5##  where A is nitro or amino and U 1 , Z and t are each as defined above. The reactive dyes are useful for dyeing hydroxyl-containing fibers such as cotton and wool and provide high yields and high wet fastness.

This application is a Continuation of application Ser. No. 07/554,860,filed on Jul. 20, 1990, now abandoned which is a continuation of U.S.application Ser. No. 07/381,941, filed Jul. 19, 1989 now abandoned.

The present invention relates to double attachment reactive dyes of theformula I ##STR6## where U¹ is C₁ -C₄ -alkyl, phenyl, C₂ -C₁₀ -alkenylor the radical ##STR7## where Q¹ and Q² are identical or different andeach is independently of the other hydrogen or C₁ -C₄ -alkyl and Q³ is agroup which is detachable under alkaline reaction conditions,

Z is the radical ##STR8## where each Q⁴ is independently of the otherhydrogen or C₁ -C₄ -alkyl which may be substituted by cyano, U² is C₁-C₄ -alkyl, phenyl, C₂ -C₁₀ -alkenyl or the radical ##STR9## where Q⁵and Q⁶ are identical or different and each is independently of the otherhydrogen or C₁ -C₄ -alkyl and Q⁷ is a group which is detachable underalkaline reaction conditions, and w is 0, 1 or 2,

t is 0, 1 or 2,

v is 0, 1 or 2,

X is a) the radical of a chromophore which may have a further reactivegroup and which is derived from a mono- or disazo dye, atriphendioxazine, an anthraquinone, a copper formazan or a metallizedphthalocyanine, or b) the radical of a coupling component which mayadditionally be linked to the radical of a diazo component via an azobridge and which may additionally have a reactive group, and

L is a) a bridge member of the formula ##STR10## where Q⁸ is hydrogen orC₁ -C₄ -alkyl, Q⁹ and Q¹⁰ are identical or different and each isindependently of the other hydrogen or C₁ -C₄ -alkyl and Q¹¹ isfluorine, chlorine or bromine, or b) an azo bridge,

with the proviso that at least one of the two radicals U¹ and U² is notC₁ -C₄ -alkyl or phenyl.

The present invention further relates to novel benzyl compounds whichserve as intermediates for these dyes.

EP-A-48,355 and EP-A-65,732 disclose double attachment reactive dyeswhich are derived from azo dyes having 1-amino-8-hydroxynaphthalene-3,6-or -4,6-disulfonic acid as the coupling component and which haveattachment components based on fluorotriazine or chlorotriazine andring-unsubstituted (sulfonylmethyl)aniline.

Earlier German Patent Application DE-A-3,731,202 relates to doubleattachment reactive dyes which are derived from metallized orunmetallized azo dyes and have a double attachment system based on atriazine/(sulfonylmethyl)aniline derivative.

It is an object of the present invention to provide novel doubleattachment reactive dyes having advantageous application properties.

We have found that this object is achieved with the novel doubleattachment reactive dyes of the above-mentioned formula I.

All the alkyl and alkenyl radicals appearing in the abovementionedformula I can be not only straight-chain but also branched.

If substituted phenyl radicals appear in the abovementioned formula I,suitable substituents are, unless otherwise stated, for example C₁ -C₄-alkyl, C₁ -C₄ -alkoxy and halogen.

Q³ and Q⁷ in the formula I are each a group which is detachable underalkaline reaction conditions. Such groups are for example chlorine, OSO₃H, SSO₃ H, OP(O)(OH)₂, C₁ -C₄ -alkylsulfonyloxy, substituted orunsubstituted phenylsulfonyloxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄-dialkylamino, ##STR11## where Q¹², Q¹³ and Q¹⁴ are identical ordifferent and each is independently of the others C₁ -C₄ -alkyl orbenzyl and each An.sup.⊖ is an anion.

U¹, U², Q¹, Q², Q⁴, Q⁵, Q⁶, Q⁸, Q⁹, Q¹⁰, Q¹², Q¹³ and Q¹⁴ in the formulaI are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutylor sec-butyl.

Q⁴ is further for example 2-cyanoethyl or 2- or 3-cyanopropyl.

U¹ and U² in the formula I are each for example 2-chloroethyl, C₂ H₄OSO₃ H, CH₂ -CH(CH₃)OSO₃ H, C₂ H₄ SSO₃ H, C₂ H₄ OP(O)(OH)₂,2-(methylsulfonyloxy)ethyl, 2-(ethylsulfonyloxy)ethyl,2-(propylsulfonyloxy)ethyl, 2-(isopropylsulfonyloxy)ethyl,2-(butylsulfonyloxy)ethyl, 2(phenylsulfonyloxy)ethyl whose phenylradical can be substituted for example by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxyor halogen, 2-(dimethylamino)ethyl, 2-(diethylamino)ethyl,2-(dipropylamino)ethyl, 2-(diisopropylamino)ethyl,2-(dibutylamino)ethyl, 2-(N-methyl-N-ethylamino)ethyl, vinyl,prop-1-en-1-yl, prop-1-en-3-yl or but-2-en-2-yl.

U¹ and U² are each further for example 2-(trimethylammonium)ethyl,2-(triethylammonium)ethyl, 2-(methyldiethylammonium)ethyl,2-(tripropylammonium)ethyl, 2-(methyldipropylammonium)ethyl,2-(tributylammonium)-ethyl, 2-(benzyldimethylammonium)ethyl,2-(benzyl-diethylammonium)ethyl, 2-pyridiniumethyl or 2-(2-, 3- or4-carboxylatopyridinium)ethyl, in which case (except for the 2-(2-, 3-or 4-carboxylatopyridinium)ethyl radical, which is present as a betaine)a suitable anion Ar.sup.⊖ is for example fluoride, chloride, bromide,iodide, mono-, dior trichloroacetate, methylsulfonate, phenylsulfonateor 2- or 4-methylphenylsulfonate.

The fiber-reactive double attachment radical of the formula II ##STR12##where U¹, Z and t are each as defined above, will hereinafter bereferred to as "E".

Preference is given to double attachment reactive dyes of the formula Ia

    X[--L--E.sup.1 ].sub.v                                     (Ia),

where X, L and v are each as defined above and E¹ is a radical of theformula IIa ##STR13## where Q² is hydrogen or methyl,

Q³ is OSO₃ H,

Z is the radical ##STR14## where Q⁶ is hydrogen or methyl, and t is 0 or2.

Particular preference is given to double attachment reactive dyes of theformula Ib

    X[--L--E.sup.2 ].sub.v                                     (Ib),

where X, L and v are each as defined above and E² is a radical of theformula IIb ##STR15## where Q² and Q⁶ are each independently of theother hydrogen or methyl.

Very particular preference is given to double attachment reactive dyesof the formula Ic

    X[--L--]E.sup.3 ].sub.v                                    (Ic),

where X, L and v are each as defined above and E³ is the radical of theformula IIc ##STR16##

Besides the double attachment system E, the radical X may carry furtherfiber-reactive radicals. Such radicals are derived for example fromtriazine, pyrimidine or vinylsulfonyl compounds.

X in the formula I is for example the radical of a coupling componentwhich may additionally be linked to the radical of a diazo component viaan azo bridge and which may have an additional reactive group. In thiscase, the double attachment radical E is bonded to the radical X via anazo bridge (--N═N--).

Dyes of this class conform to the formula IVa or IVb

    (E--N═N--).sub.a K                                     (IVa)

or

    E--N═N--K--N═N--D                                  (IVb),

where K is the radical of a coupling component, D is the radical of adiazo component, a is 1 or 2, and E is as defined above.

Useful dyes of this class are for example water-soluble azo dyes, inparticular monoazo dyes of the formula IVa (a=1) or disazo dyes of theformula IVb which have hydroxysulfonyl and/or carboxyl groups.

Important coupling components HK are derived for example from compoundsof the benzene, naphthalene, pyrazolone, pyridone or hydroxypyrimidineseries.

Important diazo components D-NH₂ are derived for example from compoundsof the aniline or aminonaphthalene series.

Particular preference is given to dyes of the formula V

    E.sup.1 --N═N--K.sup.1                                 (V),

where E¹ is as defined above and K¹ is the radical of a couplingcomponent of the naphthalene, pyrazole, pyridone or hydroxypyrimidineseries which may be a further fiber-reactive group.

Particular preference is further given to dyes of the formula VI##STR17## where one of the two radicals G¹ and G² is E¹ of theabovementioned meaning and the other is D¹ in the meaning of a radicalof a diazo component of the aniline or naphthalene series which may havea further fiber-reactive group, and G³ is hydroxysulfonyl in ringposition 3 or 4.

X in the formula I is further for example a metallized or unmetallizedradical of an azo dye. Suitable azo dye radicals are known per se andhave been described in large numbers, for example in K. Venkataraman,The Chemistry of Synthetic Dyes, vol. VI, Academic Press, New York,London, 1972. The azo dyes conform to the formula VII

    D--N═N--K (--N═N--D).sub.1                         (VII),

where D is the radical of a diazo component, K is the radical of acoupling component and 1 is 0 or 1.

Useful dyes are for example water-soluble azo dyes, in particularmonoazo dyes, of the formula VII (1=0) which can have hydroxysulfonyland/or carboxyl groups.

Preference is given to nonmetallized azo dyes, in particular those whichcontain sulfo and/or carboxyl groups, especially those having from 1 to6 sulfo groups.

Important azo dyes are for example those of the benzene-azo-naphthalene,benzene-azo-1-phenylpyrazol-5-one, benzene-azo-benzene,naphthalene-azo-benzene, benzene-azo-aminonaphthalene,naphthalene-azonaphthalene, naphthalene-azo-1-phenylpyrazol-5-one,benzene-azo-pyridone, benzene-azo-aminopyridine,naphthalene-azo-pyridone, naphthalene-azo-aminopyridine orstilbene-azo-benzene series.

Particular preference is given to double attachment reactive dyes of theformula VIII ##STR18## where E¹ is as defined above, L¹ is the radical##STR19## where Q¹¹ is as defined above, G⁴ is hydrogen, C₁ -C₄ -alkyl,chlorine or hydroxysulfonyl, and K¹ is the radical of a couplingcomponent of the naphthalene, pyrazolone, pyridone or hydroxypyrimidineseries which may have a further fiber-reactive group.

Particular preference is further given to double attachment reactivedyes of the formula IX ##STR20## where E¹ and L¹ are each as definedabove, G⁵ is C₁ -C₄ -alkanoyl, carbamoyl, C₁ -C₄ -mono- or-di-alkylcarbamoyl, phenylcarbamoyl or cyclohexylcarbamoyl, G⁶ ishydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, hydroxysulfonyl or chlorine,and D² is the radical of a diazo component of the aniline or naphthaleneseries which does not carry any further fiber-reactive group.

Particular preference is further given to double attachment reactivedyes of the formula X ##STR21## where D², E¹ and L¹ are each as definedabove and G³ is hydroxysulfonyl in ring position 3 or 4.

Particular preference is further given to double attachment reactivedyes of the formula XI ##STR22## where D², E¹ and L¹ are each as definedabove and the group --L--E¹ is in ring position 6 or 7.

Furthermore, useful compounds are those of the formula XII ##STR23##where D², E¹ and L¹ are each as defined above and p and r are each 0, 1or 2.

Furthermore, useful dyes are those of the formula XIII ##STR24## whereG³ is as defined above and one of the two radicals G⁷ and G⁸ is D² ofthe abovementioned meaning and the other is the radical SO₃ H ##STR25##where L¹ and E² are each as defined above.

Such aromatic radicals D of diazo components of the aniline andaminonaphthalene series which do not carry any fiber-reactive groups arederived for example from amines of the formulae XIV a-f ##STR26## wherem is 0, 1, 2 or 3,

p is 0, 1 or 2,

q is 0 or 1,

R¹ is hydrogen, methyl, ethyl, methoxy, ethoxy, acetyl, cyano, carboxyl,hydroxysulfonyl, C₁ -C₄ -alkoxycarbonyl, hydroxyl, carbamoyl, C₁ -C₄-mono- or -di-alkylcarbamoyl, fluorine, chlorine, bromine ortrifluoromethyl,

R² is hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, carboxyl,hydroxysulfonyl, acetylamino, C₁ -C₄ -alkoxycarbonyl, carbamoyl, C₁ -C₄-mono- or -di-alkylcarbamoyl, fluorine, chlorine, nitro, sulfamoyl, C₁-C₄ -mono- or -di-alkylsulfamoyl, C₁ -C₄ -alkylsulfonlyl, phenylsulfonylor phenoxy and

Y¹ is a direct bond, oxygen, sulfur or the group --NHCO--, --CONH--,--CO--, --NHSO₂ --, --SO₂ NH--, --SO₂ --, --CH═CH--, --CH₂ --CH₂ --,--CH₂ --, --NH-- or --N═N--.

Preference is given to those components where R¹ is hydrogen, methyl,methoxy, carboxyl, hydroxysulfonyl, hydroxyl or chlorine, R² ishydrogen, methyl, methoxy, carboxyl, hydroxysulfonly, acetylamino orchlorine and Y¹ is the group --CO--, --SO₂ --, --CH═CH--, --CH₂ --CH₂--, --CH₂ -- or --N═N--.

Aromatic amines which are suitable for use as diazo components and whichconform to the formula XIVa, XIVb, XIVc or XIVd are for example aniline,2-methoxyaniline, 2-methylaniline, 4-chloro-2-aminoanisole,4-methylaniline, 4-methoxyaniline, 2-methoxy-5-methylaniline,2,5-dimethoxyaniline, 2,5-dimethylaniline, 2,4-dimethylaniline,4-butylaniline, 2,5-diethoxyaniline, 2-chloroaniline, 3-chloroaniline,4-chloroaniline, 2,5-dichloroaniline, 4-chloro-2-nitroaniline,4-chloro-2-methylaniline, 3-chloro-2-methylaniline,4-chloro-2-aminotoluene, 4-(p-tolylsulfonyl)aniline,2-ethoxy-1-naphthylamine, 1-naphthylamine, 2-naphthylamine,4-benzoylamino-2ethoxyaniline, 4-methylsulfonylaniline,2,4-dichloroaniline-5-carboxylic acid, 2-aminobenzoic acid,4-aminobenzoic acid, 3-aminobenzoic acid, 3-chloroaniline-6-carboxylicacid, aniline-2- or -3- or -4-sulfonic acid, aniline-2,5-disulfonicacid, aniline-2,4-disulfonic acid, aniline-3,5-disulfonic acid,2-aminotoluene-4-sulfonic acid, 2-aminoanisole-4-sulfonic acid,2-aminoanisole-5-sulfonic acid, 2-ethoxyaniline-5-sulfonic acid,2-ethoxyaniline-4-sulfonic acid, 4-hydroxysulfonyl-2-aminobenzoic acid,2,5-dimethoxyaniline-4-sulfonic acid, 2,4-dimethoxyaniline-5-sulfonicacid, 2-methoxy-5-methylaniline-4-sulfonic acid,4-aminoanisole-3-sulfonic acid, 4-aminotoluene-3-sulfonic acid,2-aminotoluene-5-sulfonic acid, 2-chloroaniline-4-sulfonic acid,2-chloroaniline-5-sulfonic acid, 2-bromoaniline-4-sulfonic acid,2,6-dichloroaniline-4-sulfonic acid, 2,6-dimethylaniline-3-or-4-sulfonic acid, 3-acetylamino-6-sulfonic acid,4-acetylamino-2-hydroxysulfonylaniline, 1-aminonaphthalene-4-sulfonicacid, 1-aminonaphthalene-3-sulfonic acid, 1-aminonaphthalene-5-sulfonicacid, 1-aminonaphthalene-6-sulfonic acid, 1-aminonaphthalene-7-sulfonicacid, 1-aminonaphthalene-3,7-disulfonic acid,1-aminonaphthalene-3,6,8-trisulfonic acid,1-aminonaphthalene-4,6,8-trisulfonic acid, 2-naphthylamine-5-sulfonicacid or -6- or -8-sulfonic acid, 2-aminonaphthalene-3,6,8-trisulfonicacid, 2-aminonaphthalene-6,8-disulfonic acid,2-aminonaphthalene-1,6-disulfonic acid, 2-aminonaphthalene-1-sulfonicacid, 2-aminonaphthalene-1,5-disulfonic acid,2-aminonaphthalene-3,6-disulfonicacid,2-aminonaphthalene-4,8-disulfonicacid, 2-aminophenol-4-sulfonic acid, 2-aminophenol-5-sulfonic acid,3-aminophenol-6-sulfonic acid,1-hydroxy-2-aminonaphthalene-5,8-or-4,6-disulfonic acid,4-aminodiphenylamine, 4-amino-4'-methoxydiphenylamine,4-amino-4'-methoxydiphenylamine-3-sulfonic acid,4-(2'-methylphenylazo)-2-methylaniline, 4-aminoazobenzene,4'-nitrophenylazo-1-aminonaphthalene,4-(6'-hydroxysulfonylnaphthylazo)-1-aminonaphthalene,4-(2',5'-dihydroxysulfonylphenylazo)-1-aminonaphthalene,4'-amino-3'-methyl-3-nitrobenzophenone, 4-aminobenzophenone,4-(4'-aminophenylazo)benzenesulfonic acid,4-(4'-amino-3'methoxyphenylazo)benzenesulfonic acid and2-ethoxy-1-naphthylamine-6-sulfonic acid.

Aromatic diamines which are suitable for use as tetrazo components andwhich conform to the formula XIVe or XIVf are for example1,3-diaminobenzene, 1,3-diaminobenzene-4-sulfonic acid,1,4-diaminobenzene, 1,4-diaminobenzene-2-sulfonic acid,1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene,1,3-diamino-4-methylbenzene, 1,3-diaminobenzene-5-sulfonic acid,1,3-diamino-5-methylbenzene, 1,6-diaminonaphthalene-4-sulfonic acid,2,6-diaminonaphthalene-4,8-disulfonicacid,3,3'-diaminodiphenyl sulfone,4,4'-diaminodiphenyl sulfone, 4,4'-diaminostilbene-2,2'-disulfonic acid,2,7'-diaminodiphenyl sulfone, 2,7'-diamino-4,5-disulfodiphenyl sulfone,4,4'-diaminobenzophenone, 4,4'-diamino-3,3'-dinitrobenzophenone,3,3'-diamino-4,4'-dichlorobenzophenone, 4,4'- or 3,3'-diaminobiphenyl,4,4'-diamino-3,3'-dichlorobiphenyl, 4,4'-diamino-3,3'-dimethoxy- or-3,3'-dimethyl- or -2,2'-dimethyl- or -2,2'-dichloro- or-3,3'-diethoxy-biphenyl,4,4'-diamino-3,3'-dimethyl-6,6'-dinitrobiphenyl,4,4'-diaminobiphenyl-2,2'- or -3,3'-disulfonic acid,4,4'-diamino-3,3'-dimethyl- or - 3,3'-dimethoxy- or-2,2'-dimethoxy-biphenyl-6,6'-disulfonic acid,4,4'-diamino-2,2',5,5'-tetrachlorobiphenyl,4,4'-diamino-3,3'-dinitrobiphenyl,4,4'-diamino-2,2'-dichloro-5,5'-dimethoxybiphenyl,4,4'-diaminobiphenyl-2,2'- or -3,3'-dicarboxylic acid,4,4'-diamino-3,3'-dimethylbiphenyl-5,5'-disulfonic acid,4,4'-diamino-2-nitrobiphenyl, 4,4'-diamino-3-ethoxy- and-3-hydroxy-sulfonylbiphenyl,4,4'-diamino-3,3'-dimethylbiphenyl-5-sulfonic acid,4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane,4,4'-diamino-2,2',3,3'-tetramethyldiphenylmethane,4,4'-diaminodiphenylethane,4,4'-diaminostilbene and4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid.

Aromatic radicals D of diazo components of the aniline oraminonaphthalene series which can carry a fiber-reactive radical E arederived for example from amines of the formulae XVa-c ##STR27## where L,R¹, R², p, q, Y¹ and E are each as defined above and e and f areidentical or different and each is independently of the other 0 or 1.

Aromatic amines which conform to the formula XVa, XVb or XVc are forexample 1,3-diaminobenzene, 1,3-diaminobenzene-4-sulfonic acid,1,3-diaminobenzene-4,6-disulfonic acid, 1,4-diaminobenzene,1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2,5-disulfonicacid, 1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene,1,3-diamino-4-methylbenzene, 1,4-diaminobenzene-2,6-disulfonic acid,1,5-diamino-4-methylbenzene-2-sulfonic acid,1,5-diamino-4-methoxybenzene-2-sulfonic acid,1,6-diaminonaphth-2-ol-4-sulfonic acid,1,6-diaminonaphthalene-4-sulfonic acid,2,6-diaminonaphthalene-4,8-disulfonic acid,2,6-diaminonaphth-1-ol-4,8-disulfonic acid,1,3-diaminobenzene-5-sulfonic acid, 1,3-diamino-5-methylbenzene,2,6-diaminophenol-4-sulfonic acid,5-(aminomethyl)-2-aminonaphthalene-1-sulfonic acid,5-(N-methylaminomethyl)-2-aminonaphthalene-1-sulfonic acid,4,4'-diaminostilbene-3,3-dicarboxylic acid,4-(N-methylaminomethyl)aniline-2-sulfonic acid and3-(N-methylaminomethyl)aniline-6-sulfonic acid.

The radicals K of the coupling component preferably come from theaniline, naphthalene, pyrazole, pyridine, pyrimidine, indole oracylacetarylide series and may also carry fiber-reactive groups.

Coupling components of the aniline and naphthalene series which are freeof fiber-reactive groups correspond for example to compounds of theformulae XVIa-g ##STR28## where R³ is hydrogen or C₁ -C₄ -alkyl,

R⁴ is hydrogen, C₁ -C₄ -alkyl or phenyl which may be monosubstituted ordisubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine, bromine orhydroxysulfonyl,

R⁵ is hydrogen or C₁ -C₄ -alkyl which may be substituted by hydroxyl,cyano, carboxyl, hydroxysulfonyl, hydroxysulfonyloxy, methoxycarbonyl,ethoxycarbonyl or acetoxy,

R⁶ is hydrogen, C₁ -C₄ -alkyl which may be substituted by hydroxyl,cyano, carboxyl, hydroxysulfonyl, hydroxysulfonyloxy, methoxycarbonyl,ethoxycarbonyl or acetoxy, benzyl or phenyl which may be substituted byC₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine or hydroxysulfonyl,

R⁷ is C₁ -C₆ -alkylureido, phenylureido which may be substituted bychlorine, methyl, methoxy, nitro, hydroxysulfonyl or carboxyl, C₁ -C₆-alkanoylamino, cyclohexanoylamino, benzoylamino which may besubstituted by chlorine, methyl, methoxy, nitro, hydroxysulfonyl orcarboxyl, or hydroxyl,

R⁸ is hydrogen, C₁ -C₆ -alkyl, in particular C₁ -C₄ -alkyl, which mayeach be substituted by phenyl, C₁ -C₄ -alkoxy, hydroxyl, phenoxy or C₁-C₄ -alkanoyloxy, C₅ -C₇ -cycloalkyl, hydroxysulfonylphenyl, C₁ -C₄-alkanoyl, carbamoyl, C₁ -C₄ -mono- or -di-alkylcarbamoyl,phenylcarbamoyl or cyclohexylcarbamoyl,

R⁹ is methoxy, ethoxy, chlorine, bromine, acetylamino, amino, ureido,methylsulfonylamino, ethylsulfonylamino, dimethylaminosulfonylamino,methylamino, ethylamino, dimethylamino or diethylamino,

R¹⁰ is hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine or bromine,and

p and m are each as defined above.

Specific examples are aniline-N-methanesulfonate, o- or m-toluidine, o-or m-anisidine, cresidine, 2,5-dimethylaniline, 2,5-dimethoxyaniline,m-aminoacetanilide, 3-amino-4-methoxyacetanilide,3-amino-4-methylacetanilide, m-aminophenylurea, N-methylaniline,N-methyl-m-toluidine, N-ethylaniline, N-ethyl-m-toluidine,N-(2-hydroxyethyl)aniline and N-(2-hydroxyethyl)-m-toluidine.

Naphtholsulfonic acids are for example 1-naphthol-3-sulfonic acid,1-naphthol-4-sulfonic acid, 1-naphthol-5-sulfonic acid,1-naphthol-8-sulfonic acid, 1-naphthol-3,6-disulfonic acid,1-naphthol-3,8-disulfonic acid, 2-naphthol-5-sulfonic acid,2-naphthol-6-sulfonic acid, 2-naphthol-7-sulfonic acid,2-naphthol-8-sulfonic acid, 2-naphthol-3,6-disulfonic acid,2-naphthol-6,8-disulfonic acid, 2-naphthol-3,6,8-trisulfonic acid,1,8-dihydroxynaphthalene-3,6-disulfonic acid,2,6-dihydroxynaphthalene-8-sulfonic acid and2,8-dihydroxynaphthalene-6-sulfonic acid.

Further examples are 1-naphthylamine, N-phenyl-1-napthtylamine,N-ethyl-1-naphthylamine, N-phenyl-2-naphthylamine,1,5-naphthylenediamine, 1,8-naphthylenediamine, 1-naphthol, 2-naphthol,1,5-dihydroxynaphthalene,1,6-dihydroxynaphthalene,1,7-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 2-hydroxynaphthalene-3-N-phenylcarboxamide,2-hydroxynaphthalene-3-N-(2'-methoxyphenyl)carboxamide and2-hydroxynaphthalene-3-N-(2',5'-dimethoxyphenyl)carboxamide.

Aminonaphthalenesulfonic acids are for example1-naphthylamine-6-sulfonicacid,l-naphthylamine-7-sulfonic acid,1-naphthylamine-8-sulfonic acid, 2-naphthylamine-3,6-disulfonic acid,2-naphthylamine-5,7-disulfonic acid and 2-naphthylamine-6,8-disulfonicacid.

Specific aminonaphtholsulfonic acids are for example1-amino-5-hydroxynaphthalene-7-sulfonic acid,1-amino-8-hydroxynaphthalene-4-sulfonic acid,1-amino-8-hydroxynaphthalene-2,4-disulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,1-amino-8-hydroxynaphthalene-4,6-disulfonic acid,2-amino-5-hydroxynaphthalene-7-sulfonic acid,2-amino-8-hydroxynaphthalene-6-sulfonic acid,2-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2-amino-5-hydroxynaphthalene-1,7-disulfonic acid,1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid,1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid,1-acetylamino-8-hydroxynaphthalene-4,6-disulfonic acid,1-benzoylamino-8-hydroxynaphthalene-4,6-disulfonic acid,1-acetylamino-5-hydroxynaphthalene-7-sulfonic acid,2-methylamino-8-hydroxynaphthalene-6-sulfonic acid,2-methylamino-8-hydroxynaphthalene-6-sulfonic acid and 2-(3'- or4'-hydroxysulfonylphenyl)amino-8-hydroxynaphthalene-6-sulfonic acid.

Of particular importance are coupling components which have sulfo and/orcarboxyl groups and which couple ortho or para to a hydroxyl and/oramino group.

Examples of such coupling components are2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid,2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid,1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid,1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid,1-acetylamino-8-hydroxynaphthalene-4,6-disulfonic acid and1-benzoylamino-8-hydroxynaphthalene-4,6-disulfonic acid.

Coupling components of the other series are for example: pyrazolones,aminopyrazoles, 2,6-diaminopyridines, pyridones, hydroxypyrimidines,aminopyrimidines indoles and acetaoacetarylides.

Coupling components of this series which are free of fiber-reactivegroups conform for example to the formulae XVIIa-f ##STR29## where T isa benzene or naphthalene nucleus,

T¹ is C₁ -C₄ -alkyl, cyclohexyl, benzyl or phenyl which ismonosubstituted or polysubstituted by fluorine, chlorine, bromine,methyl, methoxy, nitro, hydroxysulfonyl, carboxyl, acetyl, acetylamino,methylsulfonyl, sulfamoyl or carbamoyl,

R¹¹ is methyl, carboxyl, methoxycarbonyl, ethoxycarbonyl or phenyl,

R¹² is hydrogen or C₁ -C₄ -alkyl which may be substituted by methoxy,ethoxy or cyano,

R¹³ is hydrogen, methyl, hydroxysulfonylmethyl, hydroxysulfonyl, cyanoor carbamoyl,

R¹⁴ is hydrogen, C₁ -C₄ -alkyl which may be substituted by phenyl,hydroxysulfonylphenyl, hydroxyl, amino, methoxy, ethoxy, carboxyl,hydroxysulfonyl, acetylamino, benzoylamino or cyano, cyclohexyl, phenylwhich may be substituted by carboxyl, hydroxysulfonyl, benzoylamino,acetylamino, methyl, methoxy, cyano or chlorine, or amino which issubstituted by phenyl, C₁ -C₄ -alkyl, acetyl or benzoyl,

R¹⁵ is C₁ -C₄ -alkyl, phenyl, hydroxyl, cyano, acetyl, benzoyl,carboxyl, methoxycarbonyl, carbamoyl or hydroxysulfonylmethyl,

R¹⁶ is hydrogen, chlorine, bromine, acetylamino, amino, nitro,hydroxysulfonyl, sulfamoyl, methylsulfonyl, phenylsulfonyl, carboxyl,methoxycarbonyl, acetyl, benzoyl, carbamoyl, cyano orhydroxysulfonylmethyl, and R¹, R², R⁵, R⁶ and m are each as definedabove.

Pyrazolone coupling components are for example 3-methyl-, 3-carboxy- or3-(C₁ -C₄ -alkoxycarbonyl)pyrazol-5-ones which may carry in the1-position hydrogen, unsubstituted or methyl-, ethyl-, fluorine-,chlorine-, bromide-, -trifluoromethyl-, methoxy-, ethoxy-, cyano-,phenoxy-, phenylsulfonyl-, methylsulfonyl-, hydroxysulfonyl-, benzoyl-,acetyl-, acetylamino-, nitro-, hydroxyl-, carboxyl-, carbamoyl- orsulfamoyl-substituted phenyl or hydroxysulfonyl-substituted 1- or2-naphthyl. Specific examples are 1-phenyl-, 1-(2,-chlorophenyl)-,1-(2'-methoxyphenyl)-, 1-(2'-methylphenyl)-, 1-(1',5'-dichlorophenyl)-,1-(2',6'-dichlorophenyl)-, 1-(2'-methyl-6'-chlorophenyl)-,1-(2'-methoxy-5'-methylphenyl)-,1-(2'-chloro-5'-hydroxysulfonylphenyl)-,1-(2'-methoxy-5'-hydroxysulfonylphenyl)-,1-(2',5'-dichloro-4'-hydroxysulfonylphenyl)-,1-(2',5'-dihydroxysulfonylphenyl)-,1-(2'-carboxyphenyl)-,1-(3'-hydroxysulfonylphenyl)-, 1-(4'-hydroxysulfonylphenyl)- or1-(3'-sulfamoylphenyl)-3-carboxyl-pyrazol-5-one, 1-(3'- or4'-hydroxysulfonylphenyl), 1-(2' -chlorophenyl)-, 1-(2'-chloro-4'- or-5'-hydroxysulfonylphenyl)-, 1-(2'-methyl-4'-hydroxysulfonylphenyl),1-(2',5'-dichlorophenyl)-, 1-(4',8'-dihydroxysulfonyl-8-naphthyl)-or1-(6'-hydroxysulfonyl-1-naphthyl)-3-methylpyrazol-5-one,ethyl-1-phenylpyrazol-5-one-3-carboxylate, ethylpyrazol-5-one-3-carboxylate and pyrazol-5-one-3-carboxylic acid.

Other coupling components from the pyrazole series are for example1-methyl-, 1-ethyl-, 1-propyl-, 1-butyl-, 1-cyclohexyl-, 1-benzyl- or1-phenyl-5-aminopyrazole, 1-(4'-chlorophenyl)- or1-(4'-methylphenyl)-5-aminopyrazole and1-phenyl-3-methyl-5-aminopyrazole.

Acetoacetanilides are in particular acetoacetanilide itself andderivatives thereof with one or more chlorine, methyl, ethyl, methoxy,ethoxy, acetylamino, hydroxysulfonyl, carboxyl, carbamoyl or sulfamoylsubstituents in the phenyl nucleus.

Pyridine-based coupling components are for example the derivativesdescribed in DE-A-2,260,827.

Suitable pyrimidine coupling components are for example the compoundslisted in DE-A-2,202,820, DE-A-2,308,663 and DE-A-3,119,349. It is alsopossible to use barbituric acid and N-substitution products thereof.Suitable N-substituents here are in particular C₁ -C₄ -alkyl andsubstituted or unsubstituted phenyl.

Suitable indole coupling components are for example 2-methylindole,2-phenylindole, 2-phenylindole-5-sulfonic acid, 1-methyl-2-phenylindoleand 1-(2'-hydroxyethyl)-, 1-(2'-carboxyethyl)- or1-(2'-carbamoylethyl)-2-methylindole or -2-phenylindole.

Suitable pyridone coupling components are for example1-ethyl-2-hydroxy-4-methyl-5-carbamoylpyrid-6-one,1-(2'-hydroxyethyl)-2-hydroxy-4-methyl-5-carbamoylpyrid-6-one,1-phenyl-2-hydroxy-4-methyl-5-carbamoylpyrid-6-one,1-ethyl-2-hydroxy-4-methyl-5-cyanopyrid-6-one,1-ethyl-2-hydroxy-4-hydroxysulfonylmethyl-5-carbamoylpyrid-6-one,1-ethyl-2-hydroxy-4-methyl-5-hydroxysulfonylmethylpyrid-6-one,1-methyl-2-hydroxy-4-methyl-5-cyanopyrid-6-one,1-methyl-2-hydroxy-5-acetylpyrid-6-one,1,4-dimethyl-2-hydroxy-5-cyanopyrid-6-one,1,4-dimethyl-5-carbamoylpyrid-6-one,2,6-dihydroxy-4-ethyl-5-cyanopyridine,2,6-dihydroxy-4=ethyl-5-carbamoylpyridine,1-ethyl-2-hydroxy-4-methyl-5-hydroxysulfonylmethylpyrid-6-one,1-methyl-2-hydroxy-4-methyl-5-methylsulfonylpyrid-6-one and1-carboxymethyl-2-hydroxy-4-ethyl-5-phenylsulfonylpyrid-6-one.

Coupling components K of the aniline and naphthalene series whichcontain fiber-reactive groups are for example compounds of the formulaeXVIIIa-e ##STR30## where L, R³, R⁴, R⁵, R⁶, E and p are each as definedabove.

Coupling components of the pyrazolone, aminopyrazole,2,6-diaminopyridine, pyridone, hydroxy or aminopyrimidine, indole oracetoacetarylide series which contain fiber-reactive groups conform forexample to the formulae XIXa-f ##STR31## where T² is a benzene ornaphthalene nucleus,

R¹⁷ is methyl, carboxyl, methoxycarbonyl, ethoxycarbonyl or phenyl,

R¹⁸ is C₁ -C₄ -alkyl, benzyl, phenylethyl or phenyl, the phenyl nucleibeing in each case unsubstituted or substituted by fluorine, chlorine,bromine, methyl, methoxy, cyano, hydroxysulfonyl, carboxyl, acetyl,nitro, carbamoyl or sulfamoyl, and

L, R¹, R², R⁵, R⁶, R¹², R¹³, R¹⁵, R¹⁶, p and E are each as definedabove.

Pyrazolone coupling components which carry fiber-reactive radicals E arederived for example from the following pyrazolones: 1-(3'- or4'-aminophenyl)-, 1-(2'-hydroxysulfonyl-5'-aminophenyl)-,1-(2'-methoxy-5'-aminophenyl)-3-carboxypyrazole-5-one, 1-(3'- or4'-aminophenyl)-, 1-(3'- or 4'-nitrophenyl)-3-methylpyrazol-5-one,1-(3'- or 4'-nitrophenyl)-,1-(6'-nitro-4',8'-dihydroxysulfonylnaphth-2'-yl)-or1-(6'-amino-4',8'-dihydroxysulfonylnaphth-2'-yl)-or1-(6'-amino-4',8'-dihydroxysulfonylnaphth-2'-yl)-3-carboxypyrazol-5-one.

Instead of azo dye radicals, the dyes of the formula I can also containcorresponding metal complex dye radicals. Suitable complexing metals arein particular copper, cobalt, chromium, nickel and iron, of whichcopper, cobalt and chromium are preferred.

In the metal complex dye radicals, the metallized groups are eachpreferably disposed ortho to the azo group, for example in the form ofo,o'-dihydroxy-, o-hydroxy-o'-carboxy, o-carboxy-o'-amino- oro-hydroxy-o'-amino-azo groups.

X in the formula I is further for example the radical of a copperformazan dye. Copper formazans are known per se and described forexample in K. Venkataraman The Chemistry of Synthetic Dyes, vol. III,Academic Press, New York, London, 1970.

Particular preference is given to copper formazan dyes of the formula XX##STR32## where G⁹, G¹⁰ and G¹¹ are identical or different and each isindependently of the others hydrogen or hydroxysulfonyl,

n is 0 or 1,

w is 0 or 1 and

E¹ and L¹ are each as defined above, with the proviso that n and w arenot both 0.

A method for preparing the formazans underlying these dyes is describedfor example in earlier Patent Application DE-A-3,737,536.

X in the formula I is further for example the radical of ananthraquinone dye. Anthraquinones are known per se and described forexample in K. Venkataraman, The Chemistry of Synthetic Dyes, vol. II,Academic Press, New York, 1952.

Particular preference is given to anthraquinone dyes of the formula XXI##STR33## where L² is the radical ##STR34## where L¹, R² and T² are eachas defined above, or in particular the radical --NH--, and E¹ is asdefined above.

X in the formula I is further for example the radical of atriphendioxazine dye. Triphendioxazines are known per se and describedfor example in EP-A-141,359 and earlier Patent ApplicationDE-A-3,735,057.

Particular preference is given to triphendioxazine dyes of the formulaXXII ##STR35## where E¹ and L¹ are each as defined above,

G¹² is hydroxysulfonyl or the radical SO₂ --C₂ H₄ --OSO₃ H,

Q¹⁵ is hydrogen, imino or C₁ -C₄ -alkylimino and

Q¹⁶ is straight-chain or branched C₂ -C₄ -alkylene or phenylene.

X in the formula I is further for example the radical of a metallizedphthalocyanine dye. Phthalocyanines are known per se and described forexample in F. H. Moser, D. L. Thomas, The Phthalocyanines, vol. II, CRCPress, Boca Raton, Fla. 1983.

Particular preference is given to phthalocyanine dyes of the formulaXXIII ##STR36## where G¹³ and G¹⁴ are identical or different and each isindependently of the other hydrogen or C₁ -C₄ -alkyl,

L³ is imino or C₁ -C₄ -alkylimino,

g is 0, 1, 2 or 3,

d is 0 or 1, and L¹, E and Q¹⁶ are each as defined above.

The present invention further provides novel benzyl compounds of theformula III ##STR37## where A is nitro or amino,

U¹ is C₁ -C₄ -alkyl, phenyl, C₂ -C₁₀ -alkenyl or the radical ##STR38##where Q¹ and Q² are identical or different and each is independently ofthe other hydrogen or C₁ -C₄ -alkyl and Q³ is hydroxyl or a group whichis detachable under alkaline reaction conditions,

Z is the radical ##STR39## where each Q⁴ is independently of the otherhydrogen or C₁ -C₄ -alkyl which may be substituted by cyano, U² is C₁-C₄ -alkyl, phenyl, C₂ -C₁₀ -alkenyl or the radical ##STR40## where Q⁵and Q⁶ are identical or different and each is independently of the otherhydrogen or C₁ -C₄ -alkyl, Q⁷ is hydroxyl or a group which is detachableunder alkaline reaction conditions, w is 0, 1 or 2, and

t is 0, 1 or 2, with the proviso that at least one of the two radicalsU¹ and U² is not C₁ -C₄ -alkyl or phenyl.

Examples of Q¹, Q², Q³, Q⁴, Q⁵, Q⁶ and Q⁷ were given above.

The novel benzyl compounds, which are useful intermediates for thesynthesis of the novel double attachment reactive dyes, can be obtainedin a conventional manner as described for example in earlier PatentApplication DE-A-3,731,202.

For example, it is possible to react a compound of the formula XXIV##STR41## where Z¹ has the meanings of Z, except C₂ -C₁₀ -alkenyl, witha thioalkanol, for example 2-thiethanol, 2-methyl-2-thioethanol or1-methyl-2-thioethanol.

By reduction of the nitro to an amino group with or without oxidation ofthe sulfur atom to sulfoxide or sulfone, in either order, and subsequentesterification, for example with chlorosulfonic acid, it is possible toarrive at the benzyl sulfone of the formula XXV ##STR42## where Q¹, Q²,Z and t are each as defined above.

Compounds of the formula XXIV can be obtained for example by reacting abenzyl chloride of the formula XXVI ##STR43## with a thioalkanol,optionally oxidizing the resulting thioether, and subsequentlyesterifying it, for example with chlorosulfonic acid.

Starting from benzyl chloride XXVI it is for example also possible, bythe abovementioned methods, to replace in a single step not only thechlorine atom in the aromatic ring by the radical --S(O)_(t) --U¹ butalso the chlorine atom of the benzyl group by the radical --S(O)_(w)--U², in which case the radicals --S(O)_(t) --U¹ and --S(O)_(w) --U² areidentical and U¹, U², t and w are each as defined above.

In place of the sulfuric ester it is also possible to introduce theother radicals which are detachable under alkaline reaction conditionsin a conventional manner.

The reactive dyes of the formula I are prepared for example by reactinga suitable organic dye or a suitable dye intermediate and thefiber-reactive compound of the formula XXVII ##STR44## where Z, U¹ and tare each as defined above and A¹ is the radical ##STR45## where Q⁸, Q⁹and Q¹¹ are each as defined above, and, if dye intermediates have beenused, converting the resulting intermediate compounds into the desireddyes in a conventional manner.

If the compound X-H is a coupling component, it is possible to obtainthe dyes according to the invention for example by diazotizing thefiber-reactive double attachment system of the formula XXVIII ##STR46##where Z, U¹ and t are each as defined above, and coupling the diazoniumproduct with the coupling component X-H in a conventional manner.

The double attachment reactive dyes according to the invention areadvantageously suitable for dyeing hydroxyl-containing fibers, inparticular cotton, but also wool.

Suitable dyeing methods are the known reactive dyeing methods, inparticular exhaust methods at from 40° to 80° C. and cold pad-batchmethods. The novel dyes are notable for high yield and high wetfastness.

The Examples which follow illustrate the invention in more detail.Percentages are by weight, unless otherwise stated.

In the table examples, the abbreviations E-1 to E-8 have the followingmeanings: ##STR47##

EXAMPLE 1

A solution of 24.2 g of4-(2'-sulfatoethyl)-3-(2"-sulfatoethylsulfonylmethyl)aniline in 270 mlof water was diazotized with 30 ml of 5N hydrochloric acid and 15 ml of3.33N NaNO₂ solution at from 0° to 5° C. and admixed with a neutralaqueous solution of 14.2 g of 1-(4-sulfophenyl)-3-carboxy-5-pyrazolone.Sodium bicarbonate was sprinkled in to maintain a pH of from 5 to 6.After the coupling had ended, the dye was salted out with potassiumchloride and gently dried under reduced pressure. It dyes cotton inlight-fast yellow shades and conforms to the formula ##STR48## Furtherdyes according to the invention, which were obtaine din a similarmanner, are given in Table 1:

                                      TABLE 1                                     __________________________________________________________________________    ENNK                                                                          Example                                                                       No.  E   K                    Hue on cotton                                   __________________________________________________________________________     2   E-1                                                                                ##STR49##           greenish yellow                                  3   E-1                                                                                ##STR50##           greenish yellow                                  4   E-1                                                                                ##STR51##           greenish yellow                                  5   E-5                                                                                ##STR52##           yellow                                           6   E-7                                                                                ##STR53##           yellow                                           7   E-1                                                                                ##STR54##           orange                                           8   E-2                                                                                ##STR55##           orange                                           9   E-3                                                                                ##STR56##           orange                                          10   E-4                                                                                ##STR57##           orange                                          11   E-1                                                                                ##STR58##           orange                                          12   E-2                                                                                ##STR59##           orange                                          13   E-1                                                                                ##STR60##           reddish orange                                  14   E-2                                                                                ##STR61##           reddish orange                                  15   E-1                                                                                ##STR62##           greenish yellow                                 16   E-1                                                                                ##STR63##           yellow                                          17   E-1                                                                                ##STR64##           greenish yellow                                 18   E-1                                                                                ##STR65##           reddish orange                                  __________________________________________________________________________

EXAMPLE 19

13 g of4-(2'-hydroxyethylsulfonyl)-3-(2"-hydroxyethylsulfonylmethyl)anilinewere dissolved in p200 ml of water at 60° C., admixed with 13.5 ml of3.33 N NaNO₂ solution, and added to a mixture of 400 g of ice and 30 mlof 5 NHCl in the course of 30 minutes. After the diazotization hadended, the resulting solution was added in the course of one hour to asolution of 15.5 g of1-hydroxy-7-(3'-sulfophenylamino)naphthalene-3-sulfonic acid in 200 mlof aqueous sodium hydroxide solution while a pH of from 8 to 8.5 wasmaintained by the simultaneous addition of 50 ml of sodium carbonatesolution. The resulting solution was evaporated down, and the residuewas dried at 60° C. under reduced pressure. The residue was suspended in200 ml of anhydrous N-methylpyrrolidone, and 19 g of chlorosulfonic acidwere added dropwise. After stirring at 50° C. for 11 hours the mixturewas discharged onto ice, the resulting mixture was brought to pH 6 withsodium bicarbonate, and precipitated sodium sulfate was filtered offwith suction at from 0° to 5° C. The filtrate was evaporated, 1-propanolwas added, the mixture was filtered off with suction, and the residuewas gently dried under reduced pressure. The dye obtained conforms tothe formula ##STR66## and dyes cotton in fast brown shades.

EXAMPLE 20

24.9 g of4-(sulfatoethylsulfonyl)-3-(2"-sulfatopropylsulfonylmethyl)aniline in480 ml of water were diazotized in the presence of hydrochloric acid atfrom 0° to 5° C. and admixed with a neutral aqueous solution of 21.2 gof 1-benzoylamino-8-hydroxynaphthalene-4,6-disulfonic acid. The couplingwas completed at pH 5-6 by sprinkling in sodium bicarbonate, and the dyeformed was salted out with potassium chloride and gently dried underreduced pressure. It dyes cotton in brilliant red shades having goodfastness properties and conforms to the formula ##STR67##

Further dyes according to the invention are given in Table 2.

                                      TABLE 2                                     __________________________________________________________________________    ENNK                                                                          Example                                                                       No.  E  K                           Hue on cotton                             __________________________________________________________________________    21   E-1                                                                               ##STR68##                  red                                       22   E-2                                                                               ##STR69##                  red                                       23   E-3                                                                               ##STR70##                  red                                       24   E-5                                                                               ##STR71##                  red                                       25   E-8                                                                               ##STR72##                  bluish red                                26   E-1                                                                               ##STR73##                  bluish red                                27   E-1                                                                               ##STR74##                  red                                       28   E-1                                                                               ##STR75##                  red                                       29   E-1                                                                               ##STR76##                  orange                                    30   E-2                                                                               ##STR77##                  orange                                    31   E-1                                                                               ##STR78##                  orange                                    32   E-1                                                                               ##STR79##                  orange                                    33   E-1                                                                               ##STR80##                  red                                       __________________________________________________________________________

EXAMPLE 34

8.4 g of4-(2'-sulfatoethylsulfonyl)-3-(2"-sulfatoethylsulfonylmethyl)anilinewere dissolved in 200 ml of H₂ O at pH 6 with NaHCO₃ and diazotized at0° C. with 3.2 ml of 5N NaNO₂ solution, 2 ml of formic acid and 3 ml of10N HCl. To this solution was added dropwise a suspension of 5.6 g of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 100 ml of H₂ O atpH 1. Stirring was continued for 4 hours, the mixture was cooled down to10° C., and 8.4 g of4-(2'-sulfatoethylsulfonyl)-3-(2'-sulfatoethylsulfonylmethyl)aniline(diazotized as described above) were added dropwise, and coupling waseffected at pH 4-4.5 using sodium bicarbonate. Stirring was continuedovernight, and the dye was salted out with KCl and gently dried. It hasthe formula ##STR81## and dyes cotton in navy shades having goodfastness properties.

EXAMPLE 35

7 g of sulfanilamide were dissolved in 200 ml of H₂ O and diazotized at0° C. with 8 ml of 5N sodium nitrite solution and 10 ml of 10Nhydrochloric acid in the course of 1 hour. A suspension of 13.7 g of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (Na salt) in 100 ml ofwater was added dropwise. The pH was 2.5. Stirring was continuedovernight at room temperature.

This was followed by the dropwise addition at 10° C. of a diazonium saltsolution prepared as follows: 21 g of4-(2'-sulfatoethylsulfonyl)-3-(2"-sulfatoethylsulfonylmethyl)aniline (Nasalt), dissolved in 200 ml of cold H₂ O at pH 6 with sodium bicarbonate,were diazotized with 8 ml of 5N sodium nitrite solution, 5 ml of formicacid and 7 ml of 10N hydrochloric acid at from 0° to 5° C. for 1 hour.

The pH was maintained at 4.5-5 with sodium bicarbonate for 2 hours, andpotassium chloride was added for salting out. The precipitate wasfiltered off with suction and dried, leaving a black powder which dyescotton in navy shades of good light fastness. The dye conforms to theformula ##STR82## Further dyes according to the invention are given inTable 3.

                                      TABLE 3                                     __________________________________________________________________________     ##STR83##                                                                    Example                                            Position                                                                           Hue on                No.  D.sup.1            D.sup.2                    3 or                                                                               cotton                __________________________________________________________________________    36                                                                                  ##STR84##         E-2                        3    navy                  37                                                                                  ##STR85##         E-2                        3    navy                  38                                                                                  ##STR86##         E-5                        3    navy                  39                                                                                  ##STR87##         E-1                        3    navy                  40   E-2                E-2                        3    navy                  41   E-3                E-3                        3    navy                  42   E-1                                                                                               ##STR88##                 3    navy                  43   E-1                                                                                               ##STR89##                 3    navy                  44   E-2                                                                                               ##STR90##                 3    navy                  45   E-1                                                                                               ##STR91##                 3    navy                  46   E-1                                                                                               ##STR92##                 4    navy                  47   E-1                                                                                               ##STR93##                 3    navy                  48   E-2                                                                                               ##STR94##                 3    navy                  49   E-1                                                                                               ##STR95##                 3    navy                  50   E-2                                                                                               ##STR96##                 3    navy                  51   E-1                                                                                               ##STR97##                 3    navy                  52                                                                                  ##STR98##         E-5                        3    reddish navy          53   E-1                E-1                        4    navy                  54   E-2                E-2                        4    navy                  55                                                                                  ##STR99##         E-1                        3    navy                  56                                                                                  ##STR100##        E-1                        3    navy                  57                                                                                  ##STR101##        E-1                        3    navy                  58                                                                                  ##STR102##        E-1                        3    navy                  59   E-1                                                                                               ##STR103##                3    navy                  60   E-5                E-1                        3    navy                  61   E-2                                                                                               ##STR104##                3    navy                  62                                                                                  ##STR105##        E-6                        3    navy                  63   E-6                                                                                               ##STR106##                3    navy                  64                                                                                  ##STR107##        E-1                        3    navy                  65   E-1                                                                                               ##STR108##                3    navy                  66                                                                                  ##STR109##        E-1                        3    navy                  67   E-3                                                                                               ##STR110##                3    navy                  68                                                                                  ##STR111##        E-1                        4    navy                  69                                                                                  ##STR112##        E-1                        4    navy                  70                                                                                  ##STR113##        E-1                        4    navy                  __________________________________________________________________________

EXAMPLE 71

24.2 g of4-(2'-sulfatoethylsulfonyl)-5-(2"-sulfatoethylsulfonylmethyl)anilinewhich had been diazotized in the presence of hydrochloric acid, in 300ml of water, were added at from 0° to 5° C. to a neutral solution in 800ml of water of 25.4 g of the secondary condensation product ofaniline-3-sulfonic acid, 2,4,6-trifluoro-1,3,5-triazine and2-amino-5-hydroxynaphthalene-7-sulfonic acid. Sodium bicarbonate wasadded to bring about a pH of 5-6, and the resulting dye was salted outwith sodium chloride. Gentle drying left a reddish orange powder whichdyes cotton in brilliant orange shades. The dye conforms to the formula##STR114##

EXAMPLE 72

24.9 parts of4-(2'-sulfatoethylsulfonyl)-3-(2"-sulfatopropylsulfonylmethyl)anilinewhich had been diazotized in the presence of hydrochloric acid, in 300ml of water, were added to a neutral solution of 30.2 g of the secondarycondensation product of 1-amino-8-hydroxynaphthalene-3,6-disulfonicacid, cyanuric chloride and aniline-4-sulfonic acid in 700 ml of water.Sodium bicarbonate was added to complete the coupling at pH 5-6. The dyeformed was salted out with sodium chloride and gently dried. It conformsto the formula ##STR115## and dyes cotton in brilliant red shades havinggood fastness properties.

The method of Examples 71 and 72 was also used to prepare the dyeslisted in Table 4.

                                      TABLE 4                                     __________________________________________________________________________     ##STR116##                                                                   Ex. No.                                                                            E  K                 X R          Hue on cotton                          __________________________________________________________________________    73   E-2                                                                               ##STR117##       Cl                                                                              OCH.sub.3  red                                    74   E-2                                                                               ##STR118##       F                                                                                ##STR119##                                                                              red                                    75   E-1                                                                               ##STR120##       Cl                                                                              OCH.sub.2 CH.sub.2 OCH.sub.3                                                             red                                    76   E-1                                                                               ##STR121##       Cl                                                                               ##STR122##                                                                              orange                                 77   E-1                                                                               ##STR123##       Cl                                                                               ##STR124##                                                                              yellow                                 78   E-2                                                                               ##STR125##       Cl                                                                               ##STR126##                                                                              yellow                                 79   E-1                                                                               ##STR127##       F                                                                                ##STR128##                                                                              yellow                                 80   E-1                                                                               ##STR129##       Cl                                                                               ##STR130##                                                                              greenish yellow                        __________________________________________________________________________

EXAMPLE 81

A neutral aqueous solution of 24.2 g of4-(2'-sulfatoethylsulfonyl)-3-(2"-sulfatoethylsulfonylmethyl)-aniline in650 ml of water was admixed with a suspension of 9.5 g of cyanuricchloride in 150 ml of ice water by stirring at from 0° to 5° C. for 1hour during which a pH of from 5-6 was maintained by addition of sodiumbicarbonate. After filtration, the filtrate was added to a solution of9.5 g of 1,3-diaminobenzene-4-sulfonic acid in 100 ml of water stirredat 40° C. and pH 5-6, and the resulting mixture was maintained at from0° to 5° C. and pH 5-6 for 2 hours.

After the reaction had ended, the diazonium salt was formed at from 0°to 5° C. by addition of 15 ml of 3.33N NaNO₂ and 30 ml of 5Nhydrochloric acid and coupled onto 11.1 g of1,4-dimethyl-3-sulfomethyl-6-hydroxy-2-pyridone. The dye obtained wassalted out with sodium chloride and gently dried under reduced pressure.It dyes cotton in brilliant fast greenish yellow shades and conforms tothe formula ##STR131##

EXAMPLE 82

33 g of the sodium salt of the dye of the formula ##STR132## weredissolved in water at pH 6 and 40° C. and admixed with 31.6 g of thecondensation product of cyanuric chloride and4-(2'-sulfatoethylsulfonyl)-3-(2"-sulfatoethylsulfonylmethyl)anilinedescribed in Example 81 and dissolved in 800 ml of water, by stirring at40° C. for a further 2 hours during which a pH of from 5-6 is maintainedby sprinkling in sodium bicarbonate. The dye, precipitated withpotassium chloride and gently dried, gives brown dyeings on cotton andconforms to the formula ##STR133##

The same method was used to obtain the dyes described in Table 5.

                                      TABLE 5                                     __________________________________________________________________________     ##STR134##                                                                   Ex. No.                                                                            E  X D             K                              Hue on                 __________________________________________________________________________                                                           cotton                  83  E-1                                                                              Cl                                                                               ##STR135##                                                                                  ##STR136##                    red                     84  E-2                                                                              F                                                                                ##STR137##                                                                                  ##STR138##                    red                     85  E-3                                                                              F                                                                                ##STR139##                                                                                  ##STR140##                    red                     86  E-1                                                                              Cl                                                                               ##STR141##                                                                                  ##STR142##                    red                     87  E-1                                                                              Cl                                                                               ##STR143##                                                                                  ##STR144##                    red                     88  E-2                                                                              Cl                                                                               ##STR145##                                                                                  ##STR146##                    red                     89  E-1                                                                              Cl                                                                               ##STR147##                                                                                  ##STR148##                    orange                  90  E-1                                                                              Cl                                                                               ##STR149##                                                                                  ##STR150##                    red                     91  E-1                                                                              Cl                                                                               ##STR151##                                                                                  ##STR152##                    yellow                  92  E-1                                                                              Cl                                                                               ##STR153##                                                                                  ##STR154##                    yellow                  93  E-1                                                                              Cl                                                                               ##STR155##                                                                                  ##STR156##                    yellow                  94  E-1                                                                              Cl                                                                               ##STR157##                                                                                  ##STR158##                    yellow                  95  E-5                                                                              Cl                                                                               ##STR159##                                                                                  ##STR160##                    yellow                  96  E-1                                                                              Cl                                                                               ##STR161##                                                                                  ##STR162##                    greenish yellow         97  E-1                                                                              Cl                                                                               ##STR163##                                                                                  ##STR164##                    greenish yellow         98  E-1                                                                              Cl                                                                               ##STR165##                                                                                  ##STR166##                    greenish yellow         99  E-1                                                                              Cl                                                                               ##STR167##                                                                                  ##STR168##                    greenish yellow        100  E-1                                                                              Cl                                                                               ##STR169##                                                                                  ##STR170##                    reddish orange         101  E-1                                                                              Cl                                                                               ##STR171##                                                                                  ##STR172##                    orange                 102  E-1                                                                              Cl                                                                               ##STR173##                                                                                  ##STR174##                    orange                 103  E-1                                                                              Cl                                                                               ##STR175##                                                                                  ##STR176##                    reddish orange         104  E-1                                                                              Cl                                                                               ##STR177##                                                                                  ##STR178##                    brown                  105  E-1                                                                              Cl                                                                               ##STR179##                                                                                  ##STR180##                    brown                  106  E-1                                                                              Cl                                                                               ##STR181##                                                                                  ##STR182##                    reddish orange         107  E-1                                                                              Cl                                                                               ##STR183##                                                                                  ##STR184##                    reddish yellow         108  E-1                                                                              Cl                                                                               ##STR185##                                                                                  ##STR186##                    reddish yellow         109  E-1                                                                              Cl                                                                               ##STR187##                                                                                  ##STR188##                    red                    110  E-1                                                                              Cl                                                                               ##STR189##                                                                                  ##STR190##                    reddish yellow         111  E-1                                                                              Cl                                                                               ##STR191##                                                                                  ##STR192##                    reddish yellow         112  E-1                                                                              Cl                                                                               ##STR193##                                                                                  ##STR194##                    orange                 113  E-1                                                                              F                                                                                ##STR195##                                                                                  ##STR196##                    orange                 114  E-1                                                                              Cl                                                                               ##STR197##                                                                                  ##STR198##                    orange                 115  E-1                                                                              Cl                                                                               ##STR199##                                                                                  ##STR200##                    orange                 116  E-1                                                                              Cl                                                                               ##STR201##                                                                                  ##STR202##                    red                    117  E-2                                                                              Cl                                                                               ##STR203##                                                                                  ##STR204##                    red                    118  E-1                                                                              Cl                                                                               ##STR205##                                                                                  ##STR206##                    greenish yellow        119  E-1                                                                              Cl                                                                               ##STR207##                                                                                  ##STR208##                    bluish red             120  E-1                                                                              Cl                                                                               ##STR209##                                                                                  ##STR210##                    red                    121  E-1                                                                              Cl                                                                               ##STR211##                                                                                  ##STR212##                    red                    122  E-1                                                                              Cl                                                                               ##STR213##                                                                                  ##STR214##                    red                    __________________________________________________________________________

EXAMPLE 123

27.7 g of the aminoazo dye obtained by coupling diazotized2-aminonaphthalene-3,6,8-trisulfonic acid onto 3-aminophenylurea weredissolved in 250 ml of water under neutral conditions and admixed at 40°C. with a neutral aqueous solution in 800 ml of water of 31.6 g of thecondensation product of cyanuric chloride and4-(2'-sulfatoethylsulfonyl)-3-(2"-sulfatoethylsulfonylmethyl)-anilineprepared as described in Example 81 by stirring for 2 hours during whicha pH of 5-6 was maintained by sprinkling in sodium bicarbonate. As soonas there were no longer any free amino groups detectable by thin layerchromatography, potassium chloride was added for salting out, and theprecipitate was gently dried under reduced pressure. The productconforms to the formula ##STR215## and dyes cotton in fast reddishyellow shades having good fastness properties.

EXAMPLE 124

The neutral aqueous solution of 31.6 g of the primary condensationproduct of cyanuric chloride and4-(2'-sulfatoethylsulfonyl)-3-(2"-sulfatoethylsulfonylmethyl)anilinedescribed in Example 81 was admixed with 15 g of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid by stirring at 40° C.for 2 hours during which a pH of 5-6 was maintained by addition ofsodium bicarbonate. The mixture was ice-cooled to 0°-5° C., 8.7 g ofdiazotized aniline-2-sulfonic acid were added, and the coupling wascompleted at pH 5-6 by addition of sodium bicarbonate. The resulting dyehas the structural formula ##STR216## and dyes cotton in fast brilliantred shades.

The same method was used to obtain the dyes listed in Table 6.

                                      TABLE 6                                     __________________________________________________________________________     ##STR217##                                                                   Ex. No.                                                                            D                          K                 X E  Hue on                 __________________________________________________________________________                                                           cotton                 125                                                                                 ##STR218##                                                                                               ##STR219##       Cl                                                                              E-1                                                                              red                    126                                                                                 ##STR220##                                                                                               ##STR221##       F E-2                                                                              red                    127                                                                                 ##STR222##                                                                                               ##STR223##       Cl                                                                              E-1                                                                              dull bluish red        128                                                                                 ##STR224##                                                                                               ##STR225##       Cl                                                                              E-1                                                                              bluish red             129                                                                                 ##STR226##                                                                                               ##STR227##       Cl                                                                              E-1                                                                              bluish red             130                                                                                 ##STR228##                                                                                               ##STR229##       Cl                                                                              E-1                                                                              red                    131                                                                                 ##STR230##                                                                                               ##STR231##       Cl                                                                              E-1                                                                              red                    132                                                                                 ##STR232##                                                                                               ##STR233##       Cl                                                                              E-1                                                                              bluish red             133                                                                                 ##STR234##                                                                                               ##STR235##       Cl                                                                              E-1                                                                              red                    134                                                                                 ##STR236##                                                                                               ##STR237##       Cl                                                                              E-1                                                                              orange                 135                                                                                 ##STR238##                                                                                               ##STR239##       Cl                                                                              E-1                                                                              orange                 136                                                                                 ##STR240##                                                                                               ##STR241##       Cl                                                                              E-1                                                                              orange                 137                                                                                 ##STR242##                                                                                               ##STR243##       Cl                                                                              E-1                                                                              orange                 138                                                                                 ##STR244##                                                                                               ##STR245##       Cl                                                                              E-2                                                                              orange                 139                                                                                 ##STR246##                                                                                               ##STR247##       Cl                                                                              E-1                                                                              yellowish red          140                                                                                 ##STR248##                                                                                               ##STR249##       Cl                                                                              E-1                                                                              yellowish red          141                                                                                 ##STR250##                                                                                               ##STR251##       Cl                                                                              E-1                                                                              yellowish red          142                                                                                 ##STR252##                                                                                               ##STR253##       Cl                                                                              E-1                                                                              red                    143                                                                                 ##STR254##                                                                                               ##STR255##       Cl                                                                              E-1                                                                              red                    144                                                                                 ##STR256##                                                                                               ##STR257##       Cl                                                                              E-1                                                                              red                    145                                                                                 ##STR258##                                                                                               ##STR259##       Cl                                                                              E-1                                                                              red                    146                                                                                 ##STR260##                                                                                               ##STR261##       Cl                                                                              E-1                                                                              red                    147                                                                                 ##STR262##                                                                                               ##STR263##       Cl                                                                              E-1                                                                              red                    148                                                                                 ##STR264##                                                                                               ##STR265##       Cl                                                                              E-1                                                                              reddish yellow         149                                                                                 ##STR266##                                                                                               ##STR267##       F E-1                                                                              reddish yellow         150                                                                                 ##STR268##                                                                                               ##STR269##       F E-1                                                                              reddish yellow         151                                                                                 ##STR270##                                                                                               ##STR271##       Cl                                                                              E-6                                                                              reddish yellow         152                                                                                 ##STR272##                                                                                               ##STR273##       Cl                                                                              E-2                                                                              reddish yellow         153                                                                                 ##STR274##                                                                                               ##STR275##       F E-3                                                                              reddish yellow         154                                                                                 ##STR276##                                                                                               ##STR277##       Cl                                                                              E-5                                                                              reddish yellow         155                                                                                 ##STR278##                                                                                               ##STR279##       Cl                                                                              E-7                                                                              reddish yellow         156                                                                                 ##STR280##                                                                                               ##STR281##       Cl                                                                              E-1                                                                              reddish yellow         157                                                                                 ##STR282##                                                                                               ##STR283##       Cl                                                                              E-1                                                                              yellow                 158                                                                                 ##STR284##                                                                                               ##STR285##       Cl                                                                              E-1                                                                              yellow                 159                                                                                 ##STR286##                                                                                               ##STR287##       Cl                                                                              E-1                                                                              reddish yellow         160                                                                                 ##STR288##                                                                                               ##STR289##       Cl                                                                              E-1                                                                              reddish yellow         161                                                                                 ##STR290##                                                                                               ##STR291##       Cl                                                                              E-1                                                                              reddish yellow         162                                                                                 ##STR292##                                                                                               ##STR293##       Cl                                                                              E-1                                                                              reddish yellow         163                                                                                 ##STR294##                                                                                               ##STR295##       F E-1                                                                              reddish yellow         164                                                                                 ##STR296##                                                                                               ##STR297##       Cl                                                                              E-1                                                                              reddish                __________________________________________________________________________                                                           yellow             

EXAMPLE 165

7 g of sulfanilamide were dissolved in 200 ml of water and admixed witha mixture of 8 ml of 5N NaNO₂ solution and 10 ml of 10N HCl at 0° C. Asuspension of 13.7 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acidin 100 ml of water was added dropwise at 0°-5° C. after 1 hour andstirred in at room temperature for 12 hours. After cooling down to 10°C., the following diazo component was added: 500 ml of aqueous solutionof 23.6 g of4-(2'-sulfatoethylsulfonyl)-3-(2'-sulfatoethylsulfonylmethyl)anilinewere admixed at 0° C. with a suspension of 8.5 of cyanuric chloride in200 ml of ice water by stirring at about 0°-5° C. for 5 hours. Thisreaction mixture was slowly added to 8.2 g of1,3-phenylenediamine-4-sulfonic acid, dissolved in 150 ml of H₂ O underneutral conditions, at 40° C. The reaction solution was maintained at40° C. and pH 5-5.5 for 1 hour and then diazotized at 0° C. for 3 hourswith 8 ml of 5N NaNO₂ solution, 5 ml of formic acid and 7 ml of 10N HCl.The coupling was carried out at pH 6-7 (maintained with sodiumbicarbonate) for 3 hours and was followed by stirring overnight at pH6.5. The dye was salted out with 200 g of sodium chloride and dried. Ithas the formula ##STR298## and dyes cotton in fast navy shades.

EXAMPLE 166

Example 165 was repeated, except that the1-amino-8-hydroxynaphthalene-3,6-disulfonic acid was replaced by1-amino-8-hydroxynaphthalene-4,6-disulfonic acid, affording a dye havingsimilar properties.

Table 7 contains further dye examples prepared in a similar manner toExample 165.

                                      TABLE 7                                     __________________________________________________________________________     ##STR299##                                                                   Ex.                         Position             Hue on                       No.                                                                              D.sup.1                  3/4  D.sup.2   X  E  cotton                       __________________________________________________________________________    167                                                                               ##STR300##              3                                                                                   ##STR301##                                                                             C1 E-1                                                                              navy                         168                                                                               ##STR302##              3                                                                                   ##STR303##                                                                             F  E-2                                                                              navy                         169                                                                               ##STR304##              3                                                                                   ##STR305##                                                                             C1 E-1                                                                              navy                         170                                                                               ##STR306##              4                                                                                   ##STR307##                                                                             C1 E-1                                                                              navy                         171                                                                               ##STR308##              3                                                                                   ##STR309##                                                                             C1 E-1                                                                              navy                         172                                                                               ##STR310##              3                                                                                   ##STR311##                                                                             C1 E-1                                                                              navy                         173                                                                               ##STR312##              3                                                                                   ##STR313##                                                                             C1 E-1                                                                              navy                         174                                                                               ##STR314##              3                                                                                   ##STR315##                                                                             C1 E-1                                                                              navy                         175                                                                               ##STR316##              3                                                                                   ##STR317##                                                                             C1 E-1                                                                              navy                         176                                                                               ##STR318##              3                                                                                   ##STR319##                                                                             C1 E-1                                                                              navy                         __________________________________________________________________________

EXAMPLE 177

13.7 g of the sodium salt of 1-amino-8-hydroxynaphthalene-3,6-disulfonicacid, suspended in 100 ml of water, were added at 0°-5° C. to thesolution of 0.04 mol of the secondary condensation product of1,3-phenylenediamine-4-sulfonic acid, cyanuric chloride and4-(2'-sulfatoethylsulfonyl)-3-(2"-sulfatoethylsulfonylmethyl)-anilineprepared and diazotized as described in Example 165. A pH of from 2.5 to3 was maintained with sodium formate. The mixture was stirred at roomtemperature for 12 hours, 7.8 g of aniline-4-sulfonic acid which hadbeen diazotized in the presence of hydrochloric acid was then added at10° C., dissolved in 200 ml of H₂ O, and the pH was maintained withsodium bicarbonate at 6-6.5. Sodium chloride was added to salt out a dyeof the formula ##STR320##

The dyes listed in Table 8 are obtained in a similar manner.

                                      TABLE 8                                     __________________________________________________________________________     ##STR321##                                                                   Ex.               Position                Hue on                              No.                                                                              E  X  D.sup.1  3/4  D.sup.2            cotton                              __________________________________________________________________________    178                                                                              E-1                                                                              F                                                                                 ##STR322##                                                                            3                                                                                   ##STR323##        navy                                179                                                                              E-1                                                                              Cl                                                                                ##STR324##                                                                            3                                                                                   ##STR325##        navy                                180                                                                              E-1                                                                              Cl                                                                                ##STR326##                                                                            3                                                                                   ##STR327##        navy                                181                                                                              E-1                                                                              Cl                                                                                ##STR328##                                                                            3                                                                                   ##STR329##        navy                                182                                                                              E-2                                                                              Cl                                                                                ##STR330##                                                                            3                                                                                   ##STR331##        navy                                183                                                                              E-3                                                                              Cl                                                                                ##STR332##                                                                            3                                                                                   ##STR333##        navy                                184                                                                              E-5                                                                              Cl                                                                                ##STR334##                                                                            3                                                                                   ##STR335##        navy                                185                                                                              E-1                                                                              Cl                                                                                ##STR336##                                                                            4                                                                                   ##STR337##        navy                                186                                                                              E-1                                                                              Cl                                                                                ##STR338##                                                                            3                                                                                   ##STR339##        navy                                187                                                                              E-1                                                                              Cl                                                                                ##STR340##                                                                            4                                                                                   ##STR341##        navy                                __________________________________________________________________________

EXAMPLE 188

38.6 g of the known dye of the formula ##STR342## were introduced firstin 400 ml of water at neutral pH and 40° C. and admixed with 31.6 g ofthe primary condensation product of cyanuric chloride and4-(2'-sulfatoethylsulfonyl)-3-(2"-sulfatoethylsulfonylmethyl)anilineprepared in Example 81, in 500 ml of water. Stirring was continued at40° C. and pH 5-6 until there were no longer any free amino groupsdetectable by thin layer chromatography. The dye obtained on salting outwith potassium chloride conforms to the formula ##STR343## and dyescotton in reddish brown shades.

Table 9 contains dyes prepared in a similar manner.

                                      TABLE 9                                     __________________________________________________________________________     ##STR344##                                                                   Ex. No.                                                                             D              K.sup.1   K.sup.2    X   E      Hue on                   __________________________________________________________________________                                                         cotton                   189                                                                                  ##STR345##                                                                                   ##STR346##                                                                              ##STR347##                                                                              Cl  E-1    reddish brown            190                                                                                  ##STR348##                                                                                   ##STR349##                                                                              ##STR350##                                                                              Cl  E-1    reddish brown            191                                                                                  ##STR351##                                                                                   ##STR352##                                                                              ##STR353##                                                                              Cl  E-1    reddish brown            192                                                                                  ##STR354##                                                                                   ##STR355##                                                                              ##STR356##                                                                              Cl  E-1    yellowish brown          193                                                                                  ##STR357##                                                                                   ##STR358##                                                                              ##STR359##                                                                              Cl  E-2    yellowish brown          194                                                                                  ##STR360##                                                                                   ##STR361##                                                                              ##STR362##                                                                              F   E-1    yellowish brown          195                                                                                  ##STR363##                                                                                   ##STR364##                                                                              ##STR365##                                                                              Cl  E-1    reddish brown            196   E.sup.1                                                                                       ##STR366##                                                                              ##STR367##                                                                              Cl                                                                                 ##STR368##                                                                          reddish brown            197                                                                                  ##STR369##                                                                                   ##STR370##                                                                              ##STR371##                                                                              Cl  E-1    reddish brown            198                                                                                  ##STR372##                                                                                   ##STR373##                                                                              ##STR374##                                                                              Cl  E-1    reddish brown            199                                                                                  ##STR375##                                                                                   ##STR376##                                                                              ##STR377##                                                                              Cl  E-1    reddish                  __________________________________________________________________________                                                         brown                

EXAMPLE 200

64.8 g of the known dye of the formula ##STR378## were suspended in 700ml of water. 31.6 g of the primary condensation product of cyanuricchloride and4-(2'-sulfatoethylsulfonyl)-3-(2"-sulfatoethylsulfonylmethyl)-anilinedescribed in Example 81 were added dissolved in 800 ml of water at pH5.5-6 and 40° C. over 2 hours, and the resulting mixture was maintainedat pH 5.5-6 and 40°-45° C. for a further 30 minutes. After the reactionhad ended, the dye was salted out with sodium chloride, filtered off anddried under reduced pressure. It conforms to the formula ##STR379## anddye cotton in fast blue shades.

EXAMPLE 201

To a suspension of 75 g of the known dichlorotriazine dye of the formula##STR380## in 600 ml of water was added at pH 7 a solution of 49 g of4-(2'-sulfatoethylsulfonyl)-3-(2"-sulfatoethylsulfonylmethyl)aniline in600 ml of water. The suspension as heated at 40°-45° C., and the pH waskept neutral by the addition of NaHCO₃. After 2.5 hours the resultingdye which conforms to the formula ##STR381## was salted out with 250 gof sodium chloride, filtered off and dried. The dark blue dye powderobtained dyes cotton in bright blue shades. The dyeings are light- andwet-fast, and they show remarkable stability to oxidative influences.

The method described in Example 201 can also be used to prepare the dyesof the formula ##STR382## listed in Table 10.

                  TABLE 10                                                        ______________________________________                                        Example  E        X      R.sup.1 R.sup.2                                                                             R.sup.3                                ______________________________________                                        202      E-2      Cl     H       SO.sub.3 H                                                                          H                                      203      E-3      Cl     H       SO.sub.3 H                                                                          H                                      204      E-1      Cl     SO.sub.3 H                                                                            H     H                                      205      E-2      Cl     SO.sub.3 H                                                                            H     H                                      206      E-3      Cl     SO.sub.3 H                                                                            H     H                                      207      E-1      Cl     SO.sub.3 H                                                                            H     SO.sub.3 H                             208      E-1      Cl     H       SO.sub.3 H                                                                          SO.sub.3 H                             ______________________________________                                    

EXAMPLE 209

43.4 g of 88% strength 1-amino-4-bromoanthraquinone-2-sulfonic acid, 39g of the amine of the formula ##STR383## 1.5 g of Cu powder, 0.75 g ofCu(II) sulfate and 50.4 g of sodium bicarbonate were heated at 65°-70°C. for 120 hours. After complete conversion (thin layer chromatography),the mixture was filtered hot, and the filtrate was brought to pH 1 withconcentrated hydrochloric acid. The oily residue was crystallized at0°-5° C. by stirring out with 100 ml of ethanol, and the crystallineproduct was isolated, washed with ethanol and dried. This gave 45 g of acompound of the formula ##STR384##

The same method can be used to obtain the compounds of the formula##STR385##

                  TABLE 11                                                        ______________________________________                                        Example No.                                                                             R             R.sup.1       n                                       ______________________________________                                        210       CH.sub.2 CH.sub.2 OH                                                                        CH.sub.2 CH.sub.2 OH                                                                        0                                       211       CH.sub.2 CH.sub.2 OH                                                                        CH.sub.2 CH.sub.2 OH                                                                        1                                       212       CH.sub.2 CH.sub.2 OH                                                                        CH.sub.2 CH(CH.sub.3)OH                                                                     0                                       213       CH.sub.2 CH.sub.2 OH                                                                        CH.sub.2 CH(CH.sub.3)OH                                                                     1                                       214       CH.sub.2 CH.sub.2 OH                                                                        CH.sub.2 CH(CH.sub.3)OH                                                                     2                                       215       CH.sub.2 CH(CH.sub.3)OH                                                                     CH.sub.2 CH.sub.2 OH                                                                        0                                       216       CH.sub.2 CH(CH.sub.3)OH                                                                     CH.sub.2 CH.sub.2 OH                                                                        1                                       217       CH.sub.2 CH(CH.sub.3)OH                                                                     CH.sub.2 CH.sub.2 OH                                                                        2                                       218       CH.sub.2 CH(CH.sub.3)OH                                                                     CH.sub.2 CH(CH.sub.3)OH                                                                     0                                       219       CH.sub.2 CH(CH.sub.3)OH                                                                     CH.sub.2 CH(CH.sub.3)OH                                                                     1                                       220       CH.sub.2 CH(CH.sub.3)OH                                                                     CH.sub.2 CH(CH.sub.3)OH                                                                     2                                       ______________________________________                                    

EXAMPLE 221

10 g of the compound of the formula ##STR386## obtained in Example 209were stirred in 40 g of chlorosulfonic acid at 20°-25° C. for 3 hours.The melt was precipitated onto 400 g of ice/water, and the mixture wasbrought to pH 5 with sodium bicarbonate. The solution was spray-dried toleave a product which, besides salt, contained the dye of the formula##STR387## Brilliant blue dyeings having good fastness properties wereobtained on cotton.

The same method can be used to obtain the dyes of the formula ##STR388##listed in Table 12.

                  TABLE 12                                                        ______________________________________                                        Example No.                                                                            R             R.sup.1        n                                       ______________________________________                                        222      CH.sub.2 CH.sub.2 OSO.sub.3 H                                                               CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                0                                       223      CH.sub.2 CH.sub.2 OSO.sub.3 H                                                               CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                1                                       224      CH.sub.2 CH.sub.2 OSO.sub.3 H                                                               CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                             0                                       225      CH.sub.2 CH.sub.2 OSO.sub.3 H                                                               CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                             1                                       226      CH.sub.2 CH.sub.2 OSO.sub.3 H                                                               CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                             2                                       227      CH.sub.2 CH.sub.3 OSO.sub.3 H                                                               CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                             0                                       228      CH.sub.2 CH.sub.3 OSO.sub.3 H                                                               CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                             1                                       229      CH.sub.2 CH.sub.3 OSO.sub.3 H                                                               CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                             2                                       230      CH.sub.2 CH.sub.3 OSO.sub.3 H                                                               CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                0                                       231      CH.sub.2 CH.sub.3 OSO.sub.3 H                                                               CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                1                                       232      CH.sub.2 CH.sub.3 OSO.sub.3 H                                                               CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                2                                       ______________________________________                                    

EXAMPLE 233

19.1 g of the compound of the formula ##STR389## were stirred into 1000g of water set to pH 10 with sodium hydroxide solution. This solutionwas added dropwise to a hot solution at 60° C. and pH 6-8 of thecondensation product of 13.5 g of cynauric chloride and 31.9 g of4-(2'-sulfatoethylsulfonyl)-5-(2"-sulfatoethylsulfonylmethyl)aniline.While a pH of 6.5-7 was maintained, stirring ws continued at 60° C.until the reaction had ended, which took about 1 hour (thin layerchromatography). After cooling down to room temperature, the dye wassalted out with 500 g of NaCl, filtered off with suction and dried. Itdyes cotton in brilliant blue shades having good fastness properties andconforms to the formula ##STR390##

Further dyes obtained in a similar manner are given in Table 13.

                                      TABLE 13                                    __________________________________________________________________________     ##STR391##                                                                   Example No.                                                                             Y           X          R E    Hue on cotton                         __________________________________________________________________________    234                                                                                      ##STR392## SO.sub.3 H Cl                                                                              E-1  blue                                  235                                                                                      ##STR393## SO.sub.3 H F E-1  blue                                  236                                                                                      ##STR394## SO.sub.3 H Cl                                                                              E-1  blue                                  237                                                                                      ##STR395## SO.sub.3 H Cl                                                                              E-1  blue                                  238                                                                                      ##STR396## SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H                                                     Cl                                                                              E-1  blue                                  239                                                                                      ##STR397## SO.sub.3 H Cl                                                                              E-1  red                                   240                                                                                      ##STR398## SO.sub.3 H Cl                                                                              E-1  red                                   241                                                                                      ##STR399## SO.sub.3 H Cl                                                                              E-2  blue                                  242                                                                                      ##STR400## SO.sub.3 H F E-2  blue                                  243                                                                                      ##STR401## SO.sub.3 H Cl                                                                              E-2  blue                                  244                                                                                      ##STR402## SO.sub.3 H Cl                                                                              E-2  blue                                  245                                                                                      ##STR403## SO.sub.3 H Cl                                                                              E-2  blue                                  246                                                                                      ##STR404## SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H                                                     Cl                                                                              E-2  blue                                  247                                                                                      ##STR405## SO.sub.3 H Cl                                                                              E-2  red                                   248                                                                                      ##STR406## SO.sub.3 H Cl                                                                              E-2  red                                   249                                                                                      ##STR407## SO.sub.3 H Cl                                                                              E-3  blue                                  250                                                                                      ##STR408## SO.sub.3 H F E-3  blue                                  251                                                                                      ##STR409## SO.sub.3 H Cl                                                                              E-3  blue                                  252                                                                                      ##STR410## SO.sub.3 H Cl                                                                              E-3  blue                                  253                                                                                      ##STR411## SO.sub.3 H Cl                                                                              E-3  blue                                  254                                                                                      ##STR412## SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H                                                     Cl                                                                              E-3  blue                                  255                                                                                      ##STR413## SO.sub.3 H Cl                                                                              E-3  red                                   256                                                                                      ##STR414## SO.sub.3 H Cl                                                                              E-3  red                                   __________________________________________________________________________

EXAMPLE 257

To a neutral solution of 48 g of4-(2'-sulfatoethylsulfonyl)-5-(2"-sulfatoethylsulfonylmethyl)aniline in200 ml of water were added at from 5°-10° C. 97 g of copperphthalocyaninetetrasulfonyl chloride as a moist presscake. The mixturewas stirred at 20°-25° C. for 12 hours while the pH was maintained at6.5-7.3 by addition of 10% strength sodium carbonate solution. Themixture was then filtered off with suction, the filter residue wasdried, leaving 47 g of the dye of the formula ##STR415## which contained2.7% of NaCl. The dye dyes cotton in greenish blue shades.

EXAMPLE 258

97 g of copper phthalocyaninetetrasulfonyl chloride were suspended in750 ml of water at 0°-5° C. 20.5 g of monoacetylethylenediamine wereadded, and the pH was maintained at 7.3-7.5 with 10% strength sodiumcarbonate solution. After 12 hours at 20°-25° C., the pH was raised to10 by addition of sodium hydroxide solution, and the mixture was stirredat 95° C. for one hour. Concentrated hydrochloric acid was added tobring down a precipitate. The precipitate was filtered off with suction,washed with about 2% strength hydrochloric acid and stirred up in 500 mlof water. The pH of the solution was brought to 7.0-7.2 with sodiumhydroxide solution, and 21.2 g of cyanuric chloride were added at 0°-5°C. The pH was maintained at 6.5-7.0 by the dropwise addition of sodiumcarbonate solution. After 3 hours 49 g of4-(2'-sulfatoethylsulfonyl)-5-(2" -sulfatoethylsulfonylmethyl)-anilinewere added, and the temperature was raised to 35°-40° C. The dyesolution was spray-dried, giving 185 g of the dye of the formula##STR416## The dye dyes cotton in greenish blue shades.

EXAMPLE 259

97 g of copper phthalocyaninetetrasulfonyl chloride were suspended in600 ml of water at 0°-5° C. 41 g of N-monoacetyl-m-phenylenediamine wereadded, and the pH was maintained at 6.8-7.0 by addition of 10% strengthsodium carbonate solution. 12 g of 25% strength ammonia solution and 16g of sodium acetate were then added, and the temperature was raised to50° C. in the course of 3 hours and the pH was maintained at 7.0. 250 gof concentrated HCl were added, and the temperature was raised to90°-95° C. After 4 hours, the mixture was cooled down, and the resultingprecipitate was filtered off with suction and washed neutral. Withoutdrying, the precipitate was suspended in 750 ml of water, and 19.4 g ofcyanuric chloride were added at pH 7.0 and 0-°5° C. The pH wasmaintained at 6.5-7.0 by the addition of sodium carbonate solution.After 3 hours 49 g of4-(2'-sulfatoethylsulfonyl)-5-(2"-sulfatoethylsulfonylmethyl)-anilinewere added, and the temperature was raised to 35°-40° C. The dyesolution was spray-dried, giving 260 g of the dye of the formula##STR417## which dyes cotton in greenish blue shades.

EXAMPLE 260

350 g of 5-nitro-2-chlorobenzyl chloride, 136 g of 2-mercaptoethanol and234.5 g of potassium carbonate were stirred in 1700 ml of water at 40°C. for 4 hours and at 60° C. for 1 hour. The reaction solution wasbrought to pH 6 with acetic acid and, after the addition of 10 g oftungstic acid, admixed with 2060 g of 15% strength hydrogen peroxidesolution at 55° C. After the exothermic reaction had ended, the mixturewas stirred at 85° C. for 3 hours and at 20° C. for 12 hours. Theprecipitated product was isolated, washed with water and dried underreduced pressure at 50° C., leaving 395 g of an analytically pureproduct of the following constitution: ##STR418##

Analysis Calc.: chlorine covalent 12.7% found: 12.4%

melting point: 127°-128° C.

If instead of 2-mercaptoethanol the same molar amount of1-mercaptopropan-2-ol was used, then an analytically pure product of theformula (260a) ##STR419##

melting point: 121°-122° C. was obtained.

The same method was used to prepare the following intermediates:##STR420##

29.8 g of 4-nitro-1-chloro-2-benzyl β-hydroxyethyl sulfone obtained inExample 260 and 3.3 g of paraformaldehyde were heated to 60° C. in 100ml of methanol. 19.8 g of 30% strength sodium methoxide solution wereadded dropwise at that temperature in the course of 0.5 hours. After 3hours' stirring at 60°-65° C. the mixture was cooled down to 20°-25° C.,and the precipitated product was isolated, washed with water and dried,leaving 20 g of an analytically pure product of the formula ##STR421##

Analysis calc.: chlorine covalent 12.2% found: 12.1%

melting point: 224° C.

EXAMPLE 262

59.5 g of 4-nitro-1-chloro-2-benzyl β-hydroxyethyl sulfone obtained inExample 260 were dissolved in 100 ml of N-methylpyrrolidinone. To thecold solution at 0° C. was added dropwise a freshly prepared solution of17.2 g of thioethanol, 12.3 g of potassium hydroxide and 100 ml ofN-methylpyrrolidinone. After 12 hours' stirring at 20°-25° C. thesolvent was distilled off under reduced pressure, 200 ml of water wereadded to the residue, and the mixture was brought to pH 6 with aceticacid. After 2 hours' stirring at 0°-5° C. the precipitated product wasisolated, washed with water ad dried, leaving 60 g of a product whichpredominantly conformed to the formula ##STR422##

melting point: 126°-128° C.

The following compounds are obtained by the method of Example 262 fromthe intermediates described in Examples 260 and 261:

                  TABLE 14                                                        ______________________________________                                         ##STR423##                                                                   Example                                                                       No.    R      R.sup.1         R.sup.2                                         ______________________________________                                        263    H      CH.sub.2 CH.sub.2 OH                                                                          CH.sub.2 CH.sub.2 OH                            264    H      CH.sub.2 CH.sub.2 OH                                                                          CH.sub.2 CH(CH.sub.3)OH                         265    H      CH.sub.2 CH.sub.2 OH                                                                          C(CH.sub.3).sub.3                               266    H      CH.sub.2 CH.sub.2 OH                                                                          Ph                                              267    H      CH.sub.2 CH(CH.sub.3)OH                                                                       CH.sub.2 CH.sub.2 OH                            268    H      CH.sub.2 CH(CH.sub.3)OH                                                                       CH.sub.2 CH(CH.sub.3)OH                         269    H      CH.sub.2 CH(CH.sub.3)OH                                                                       C(CH.sub.3).sub.3                               270    H      CH.sub.2 CH(CH.sub.3)OH                                                                       Ph                                              271    H      C(CH.sub.3).sub.3                                                                             CH.sub.2 CH.sub.2 OH                            272    H      C(CH.sub.3).sub.3                                                                             CH.sub.2 CH(CH.sub.3)OH                         273    H      Ph              CH.sub.2 CH.sub.2 OH                            274    H      Ph              CH.sub.2 CH(CH.sub.3)OH                         275           CH.sub. 2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH.sub.2 OH                            276           CH.sub.2 OCH.sub.2 CH.sub.2                                                                   CH.sub.2 CH(CH.sub.3)OH                         ______________________________________                                    

EXAMPLE 277

32.1 g of the compound of the formula ##STR424## described in Example262 were dissolved in 200 ml of water at 40° C. and oxidized by additionof 0.5 g of tungstic acid and molar amounts of hydrogen peroxide. After2 hours' stirring at 40° C., the mixture was cooled down to 0°-5° C.,and the precipitated product was isolated, washed with water and driedat 40° C. under reduced pressure, leaving 30.2 g of a product whichpredominantly conformed to the formula ##STR425##

melting point: 58°-61° c.

The same method can be used to give the compounds described in Table 15.

                  TABLE 15                                                        ______________________________________                                         ##STR426##                                                                   Example                                                                       No.    R      R.sup.1         R.sup.2                                         ______________________________________                                        278    H      CH.sub.2 CH.sub.2 OH                                                                          CH.sub.2 CH.sub.2 OH                            279    H      CH.sub.2 CH.sub.2 OH                                                                          CH.sub.2 CH(CH.sub.3)OH                         280    H      CH.sub.2 CH.sub.2 OH                                                                          C(CH.sub.3).sub.3                               281    H      CH.sub.2 CH.sub.2 OH                                                                          Ph                                              282    H      CH.sub.2 CH(CH.sub.3)OH                                                                       CH.sub.2 CH.sub.2 OH                            283    H      CH.sub.2 CH(CH.sub.3)OH                                                                       CH.sub.2 CH(CH.sub.3)OH                         284    H      CH.sub.2 CH(CH.sub.3)OH                                                                       C(CH.sub.3).sub.3                               285    H      CH.sub.2 CH(CH.sub.3)OH                                                                       Ph                                              286    H      C(CH.sub.3).sub.3                                                                             CH.sub.2 CH.sub.2 OH                            287    H      C(CH.sub.3).sub.3                                                                             CH.sub.2 CH(CH.sub.3)OH                         288    H      Ph              CH.sub.2 CH.sub.2 OH                            289    H      Ph              CH.sub.2 CH(CH.sub. 3)OH                        290           CH.sub.2 OCH.sub.2 CH.sub.2                                                                   CH.sub.2 CH.sub.2 OH                            291           CH.sub.2 OCH.sub.2 CH.sub.2                                                                   CH.sub.2 CH(CH.sub.3)OH                         ______________________________________                                    

EXAMPLE 292

59.5 g of 4-nitro-1-chloro-2-benzyl β-hydroxyethyl sulfone obtaine dinExample 260 were dissolved in 100 ml of N-methylpyrrolidinone. To thecold solution at 0° C. was added dropwise a freshly prepared solution of17.2 g of thioethanol, 12.3 g of potassium hydroxide and 100 ml ofN-methylpyrrolidinone. After 12 hours' stirring at 20°-25° C. thesolvent was distilled off under reduced pressure, and the residue wasadmixed with 200 ml of water and heated to 40° C. The solution wasbrought to pH 6 with acetic acid and, after addition of 0.8 g oftungstic acid, oxidized with the molar amount of hydrogen peroxide.After 2 hours' stirring at 40° C., the mixture was cooled down to 0°-5°C., and the precipitated product was isolated, washed with water anddried at 40° C. under reduced pressure. This left 60.9 g of a productwhich conformed to the compound of the formula ##STR427##

melting point: 58°-61° C.

described in Example 277.

The compounds described in Table 15 may also be obtained by the methoddescribed above.

EXAMPLE 293

963 g of 4-nitro-1-chloro-2-benzyl β-hydroxyethyl sulfone obtained inExample 260 were dissolved in 1500 ml of N-methylpyrrolidinone. To thecold solution at 0° C. was added dropwise a freshly prepared solution of297 g of thioethanol, 212 g of potassium hydroxide and 1500 ml ofN-methylpyrrolidinone in the course of 3 hours. After 12 hours' stirringat 20°-25° C. the solvent was distilled off under reduced pressure, andthe residue was admixed with 3000 ml of water, heated to 40° C. and,after the addition of 10 g of tungstic acid, oxidized with 2100 g of 30%strength hydrogen peroxide solution. After the exothermic reaction hadended, the mixture was stirred at 60° C. for 2 hours, at 80° C. foranother 2 hours and at 95° C. for 1 hour, and cooled down to 20°-25° C.The precipitated product was isolated, washed with water and dried at40° C. under reduced pressure, leaving 1005 g of product conforming tothe formula ##STR428##

melting point: 139°-142° C.

The intermediates described in Examples 260 and 261 can be converted bythe method of Example 293 into the compounds listed in Table 16.

                  TABLE 16                                                        ______________________________________                                         ##STR429##                                                                   Ex. No.                                                                              R      R.sup.1         R.sup.2                                         ______________________________________                                        294    H      CH.sub.2 CH.sub.2 OH                                                                          CH.sub.2 CH(CH.sub.3)OH                         295    H      CH.sub.2 CH.sub.2 OH                                                                          C(CH.sub.3).sub.3                               296    H      CH.sub.2 CH.sub.2 OH                                                                          Ph                                              297    H      CH.sub.2 CH(CH.sub.3)OH                                                                       CH.sub.2 CH.sub.2 OH                            298    H      CH.sub.2 CH(CH.sub.3)OH                                                                       CH.sub.2 CH(CH.sub.3)OH                         299    H      CH.sub.2 CH(CH.sub.3)OH                                                                       C(CH.sub.3).sub.3                               300    H      CH.sub.2 CH(CH.sub.3)OH                                                                       Ph                                              301    H      C(CH.sub.3).sub.3                                                                             CH.sub.2 CH.sub.2 OH                            302    H      C(CH.sub.3).sub.3                                                                             CH.sub.2 CH(CH.sub.3)OH                         303    H      Ph              CH.sub.2 CH.sub.2 OH                            304    H      Ph              CH.sub.2 CH(CH.sub.3).sub.3 OH                  305           CH.sub.2 OCH.sub.2 CH.sub. 2                                                                  CH.sub.2 CH.sub.2 OH                            306           CH.sub.2 OCH.sub.2 CH.sub.2                                                                   CH.sub.2 CH(CH.sub.3).sub.3 OH                  ______________________________________                                    

EXAMPLE 307

32.1 g of the compound described in Example 262 were dissolved in 100 mlof water at 40° C. and, after the addition of 0.5 g of tungstic acid,oxidized with 70 g of 30% strength hydrogen peroxide solution. After theexothermic reaction had ended, the mixture was stirred at 60° C. for 2hours and then at 80° C. for a further 2 hours. After cooling down to20°-25° C. the precipitated product was isolated, washed with water anddried at 40° C. under reduced pressure, leaving 34 g of a product whichconformed to the compound of the formula ##STR430##

melting point: 139°-142° C.

described in Example 293.

The compounds described in Table 14 can be converted by the method ofExample 307 into the compounds listed in Table 15.

EXAMPLE 308

50 g of the compound described in Example 307, 142 ml of thionylchloride, 500 ml of toluene and 2 ml of dimethylformamide were stirredat 65° C. for 1 hour and at 85° C. for 2 hours. After cooling down to5°-10° C. the precipitated product was isolated, washed with water anddried at 60° C. under reduced pressure, leaving 54 g of a productconforming to the formula ##STR431##

melting point: 158° C.

The products listed in Tables 14, 15 and 16 can be converted by themethod of Example 308 into compounds of the formula ##STR432##

                  TABLE 17                                                        ______________________________________                                        Ex. No.                                                                              R      R.sup.1        R.sup.2     n                                    ______________________________________                                        309    H      CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.2 CH.sub.2 Cl                                                                      0                                    310    H      CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.2 CH.sub.2 Cl                                                                      1                                    311    H      CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.2 CH(CH.sub.3)Cl                                                                   0                                    312    H      CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.2 CH(CH.sub.3)Cl                                                                   1                                    313    H      CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.2 CH(CH.sub.3)Cl                                                                   2                                    314    H      CH.sub.2 CH.sub.2 Cl                                                                         Ph          0                                    315    H      CH.sub.2 CH.sub.2 Cl                                                                         Ph          1                                    316    H      CH.sub.2 CH.sub.2 Cl                                                                         Ph          2                                    317    H      CH.sub.2 CH.sub.2 Cl                                                                         C(CH.sub.3).sub.3                                                                         0                                    318    H      CH.sub.2 CH.sub.2 Cl                                                                         C(CH.sub.3).sub.3                                                                         1                                    319    H      CH.sub.2 CH.sub.2 Cl                                                                          C(CH.sub.3).sub.3                                                                        2                                    320    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      CH.sub.2 CH.sub.2 Cl                                                                      0                                    321    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      CH.sub.2 CH.sub.2 Cl                                                                      1                                    322    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      CH.sub.2 CH.sub.2 Cl                                                                      2                                    323    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      CH.sub.2 CH(CH.sub.3)Cl                                                                   0                                    324    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      CH.sub.2 CH(CH.sub.3)Cl                                                                   1                                    325    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      CH.sub.2 CH(CH.sub.3)Cl                                                                   2                                    326    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      Ph          0                                    327    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      Ph          1                                    328    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      Ph          2                                    329    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      C(CH.sub.3).sub.3                                                                         0                                    330    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      C(CH.sub.3).sub.3                                                                         1                                    331    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      C(CH.sub.3).sub.3                                                                         2                                    332    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH.sub.2 Cl                                                                      0                                    333    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH.sub.2 Cl                                                                      1                                    334    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH.sub.2 Cl                                                                      2                                    335    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH(CH.sub.3)Cl                                                                   0                                    336    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH(CH.sub.3)Cl                                                                   1                                    337    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH(CH.sub.3)Cl                                                                   2                                    338    H      Ph             CH.sub.2 CH.sub.2 Cl                                                                      0                                    339    H      Ph             CH.sub.2 CH.sub.2 Cl                                                                      1                                    340    H      Ph             CH.sub.2 CH.sub.2 Cl                                                                      2                                    341    H      Ph             CH.sub.2 CH(CH.sub.3)Cl                                                                   0                                    342    H      Ph             CH.sub.2 CH(CH.sub.3)Cl                                                                   1                                    343    H      Ph             CH.sub.2 CH(CH.sub.3)Cl                                                                   2                                    344           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH.sub.2 Cl                                                                      0                                    345           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH.sub.2 Cl                                                                      1                                    346           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH.sub.2 Cl                                                                      2                                    347           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH(CH.sub.3)Cl                                                                   0                                    348           CH.sub. 2 OCH.sub.2 CH.sub.2                                                                 CH.sub.2 CH(CH.sub.3)Cl                                                                   1                                    349           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH(CH.sub.3)Cl                                                                   2                                    ______________________________________                                    

EXAMPLE 350

160 g of the compound described in Example 293 were catalyticallyreduced with Raney nickel at 25°-30° C. in 1000 ml of methanol. Afterthe reduction had ended, the Raney nickel was separated off and themethanol was distilled off, leaving the amine of the formula ##STR433##

melting point: 112°-113° C.

as an oil which crystallized at 0°-5° C. in the course of one hour.

By the same method it is possible to obtain the following amines of theformula: ##STR434##

                  TABLE 18                                                        ______________________________________                                        Ex. No.                                                                              R      R.sup.1        R.sup.2     n                                    ______________________________________                                        351    H      CH.sub.2 CH.sub.2 OH                                                                         CH.sub.2 CH.sub.2 OH                                                                      0                                    352    H      CH.sub.2 CH.sub.2 OH                                                                         CH.sub.2 CH.sub.2 OH                                                                      1                                    353    H      CH.sub.2 CH.sub.2 OH                                                                         CH.sub.2 CH(CH.sub.3)OH                                                                   0                                    354    H      CH.sub.2 CH.sub.2 OH                                                                         CH.sub.2 CH(CH.sub.3)OH                                                                   1                                    355    H      CH.sub.2 CH.sub.2 OH                                                                         CH.sub.2 CH(CH.sub.3)OH                                                                   2                                    356    H      CH.sub.2 CH.sub.2 OH                                                                         Ph          0                                    357    H      CH.sub.2 CH.sub.2 OH                                                                         Ph          1                                    358    H      CH.sub.2 CH.sub.2 OH                                                                         Ph          2                                    359    H      CH.sub.2 CH.sub.2 OH                                                                         C(CH.sub.3).sub.3                                                                         0                                    360    H      CH.sub.2 CH.sub.2 OH                                                                         C(CH.sub.3).sub.3                                                                         1                                    361    H      CH.sub.2 CH.sub.2 OH                                                                         C(CH.sub.3).sub. 3                                                                        2                                    362    H      CH.sub.2 CH(CH.sub.3)OH                                                                      CH.sub.2 CH.sub.2 OH                                                                      0                                    363    H      CH.sub.2 CH(CH.sub.3)OH                                                                      CH.sub.2 CH.sub.2 OH                                                                      1                                    364    H      CH.sub.2 CH(CH.sub.3)OH                                                                      CH.sub.2 CH.sub.2 OH                                                                      2                                    365    H      CH.sub.2 CH(CH.sub.3)OH                                                                      CH.sub.2 CH(CH.sub.3)OH                                                                   0                                    366    H      CH.sub.2 CH(CH.sub.3)OH                                                                      CH.sub.2 CH(CH.sub.3)OH                                                                   1                                    367    H      CH.sub.2 CH(CH.sub.3)OH                                                                      CH.sub.2 CH(CH.sub.3)OH                                                                   2                                    368    H      CH.sub.2 CH(CH.sub.3)OH                                                                      Ph          0                                    369    H      CH.sub.2 CH(CH.sub.3)OH                                                                      Ph          1                                    370    H      CH.sub.2 CH(CH.sub.3)OH                                                                      Ph          2                                    371    H      CH.sub.2 CH(CH.sub.3)OH                                                                      C(CH.sub.3).sub.3                                                                         0                                    372    H      CH.sub.2 CH(CH.sub.3)OH                                                                      C(CH.sub.3).sub.3                                                                         1                                    373    H      CH.sub.2 CH(CH.sub.3)OH                                                                      C(CH.sub.3).sub.3                                                                         2                                    374    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH.sub.2 OH                                                                      0                                    375    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH.sub.2 OH                                                                      1                                    376    H      C(CH.sub.3 ).sub.3                                                                           CH.sub.2 CH.sub.2 OH                                                                      2                                    377    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH(CH.sub.3)OH                                                                   0                                    378    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH(CH.sub.3)OH                                                                   1                                    379    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH(CH.sub.3)OH                                                                   2                                    380    H      Ph             CH.sub.2 CH.sub.2 OH                                                                      0                                    381    H      Ph             CH.sub.2 CH.sub.2 OH                                                                      1                                    382    H      Ph             CH.sub.2 CH.sub.2 OH                                                                      2                                    383    H      Ph             CHCH(CH.sub.3)OH                                                                          0                                    384    H      Ph             CHCH(CH.sub.3)OH                                                                          1                                    385    H      Ph             CHCH(CH.sub.3)OH                                                                          2                                    386    H      CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.2 CH.sub.2 Cl                                                                      0                                    387    H      CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.2 CH.sub.2 Cl                                                                      1                                    388    H      CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.2 CH.sub.2 Cl                                                                      2                                    389    H      CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.2 CH(CH.sub.3)Cl                                                                   0                                    390    H      CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.2 CH(CH.sub.3)Cl                                                                   1                                    391    H      CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.2 CH(CH.sub.3)Cl                                                                   2                                    392    H      CH.sub.2 CH.sub.2 Cl                                                                         Ph          0                                    393    H      CH.sub.2 CH.sub.2 Cl                                                                         Ph          1                                    394    H      CH.sub.2 CH.sub.2 Cl                                                                         Ph          2                                    395    H      CH.sub.2 CH.sub.2 Cl                                                                         C(CH.sub.3).sub.3                                                                         0                                    396    H      CH.sub.2 CH.sub.2 Cl                                                                         C(CH.sub.3).sub.3                                                                         1                                    397    H      CH.sub.2 CH.sub.2 Cl                                                                         C(CH.sub.3).sub.3                                                                         2                                    398    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      CH.sub.2 CH.sub.2 Cl                                                                      0                                    399    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      CH.sub.2 CH.sub.2 Cl                                                                      1                                    400    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      CH.sub.2 CH.sub.2 Cl                                                                      2                                    401    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      CH.sub.2 CH(CH.sub.3)Cl                                                                   0                                    402    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      CH.sub.2 CH(CH.sub.3)Cl                                                                   1                                    403    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      CH.sub.2 CH(CH.sub.3)Cl                                                                   2                                    404    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      Ph          0                                    405    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      Ph          1                                    406    H      CH.sub.2 CH(CH.sub.3)Cl                                                                       Ph         2                                    407    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      C(CH.sub.3).sub.3                                                                         0                                    408    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      C(CH.sub.3).sub.3                                                                         1                                    409    H      CH.sub.2 CH(CH.sub.3)Cl                                                                      C(CH.sub.3).sub.3                                                                         2                                    410    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH.sub.2 Cl                                                                      0                                    411    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH.sub.2 Cl                                                                      1                                    412    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH.sub.2 Cl                                                                      2                                    413    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH(CH.sub.3)Cl                                                                   0                                    414    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH(CH.sub.3)Cl                                                                   1                                    415    H      C(CH.sub.3).sub.3                                                                            CH.sub.2 CH(CH.sub.3)Cl                                                                   2                                    416    H      Ph             CH.sub.2 CH.sub.2 Cl                                                                      0                                    417    H      Ph             CH.sub.2 CH.sub.2 Cl                                                                      1                                    418    H      Ph             CH.sub.2 CH.sub.2 Cl                                                                      2                                    419    H      Ph             CH.sub.2 CH(CH.sub.3)Cl                                                                   0                                    420    H      Ph             CH.sub.2 CH(CH.sub.3)Cl                                                                   1                                    421    H      Ph             CH.sub.2 CH(CH.sub.3)Cl                                                                   2                                    422           CH.sub.2 O CH.sub.2 CH.sub.2                                                                 CH.sub.2 CH.sub.2 OH                                                                      0                                    423           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH.sub.2 OH                                                                      1                                    424           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH.sub.2 OH                                                                      2                                    425           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH(CH.sub.3)OH                                                                   0                                    426           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH(CH.sub.3)OH                                                                   1                                    427           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH(CH.sub.3)OH                                                                   2                                    428           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH.sub.2 Cl                                                                      0                                    429           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH.sub.2 Cl                                                                      1                                    430           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH.sub.2 Cl                                                                      2                                    431           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH(CH.sub.3)Cl                                                                   0                                    432           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH(CH.sub. 3)Cl                                                                  1                                    433           CH.sub.2 OCH.sub.2 CH.sub.2                                                                  CH.sub.2 CH(CH.sub.3)Cl                                                                   2                                    ______________________________________                                    

EXAMPLE 434

90 g of the compound of the formula ##STR435## were added at 0°-10° C.to 360 g of chlorosulfonic acid and the mixture was stirred at 20°-25°C. for 5 hours. The mixture was discharged onto 900 ml of ice-water, andspontaneous crystallization took place. The precipitate was filteredoff, washed with acetone until free of sulfuric acid and dried. Theyield was almost quantitative. The product conformed to the formula##STR436## By the same method it is possible to obtain the compoundslisted in Table 19.

                  TABLE 19                                                        ______________________________________                                         ##STR437##                                                                   Ex-                                                                           am-                                                                           ple                                                                           No.  R     R.sup.1         R.sup.2       n                                    ______________________________________                                        435  H     CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                 C(CH.sub.3).sub.3                                                                           0                                    436  H     CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                 C(CH.sub.3).sub.3                                                                           1                                    437  H     CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                 C(CH.sub.3).sub.3                                                                           2                                    438  H     CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                 Ph            0                                    439  H     CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                 Ph            1                                    440  H     CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                 Ph            2                                    441  H     CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              C(CH.sub.3).sub.3                                                                           0                                    442  H     CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              C(CH.sub.3).sub.3                                                                           1                                    443  H     CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              C(CH.sub.3).sub.3                                                                           2                                    444  H     CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              Ph            0                                    445  H     CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              Ph            1                                    446  H     CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              Ph            2                                    447  H     C(CH.sub.3).sub.3                                                                             CH.sub.2 CH.sub.2 OSO.sub.3 H                                                               0                                    448  H     C(CH.sub.3).sub.3                                                                             CH.sub.2 CH.sub.2 OSO.sub.3 H                                                               1                                    449  H     C(CH.sub.3).sub.3                                                                             CH.sub.2 CH.sub.2 OSO.sub.3 H                                                               2                                    450  H     C(CH.sub.3).sub.3                                                                             CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                            0                                    451  H     C(CH.sub.3).sub.3                                                                             CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                            1                                    452  H     C(CH.sub.3).sub.3                                                                             CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                            2                                    453  H     Ph              CH.sub.2 CH.sub.2 OSO.sub.3 H                                                               0                                    454  H     Ph              CH.sub.2 CH.sub.2 OSO.sub.3 H                                                               1                                    455  H     Ph              CH.sub.2 CH.sub.2 OSO.sub.3 H                                                               2                                    456  H     Ph              CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                            0                                    457  H     Ph              CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                            1                                    458  H     Ph              CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                            2                                    459        CH.sub.2 OCH.sub.2 CH.sub.2                                                                   CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                            0                                    460        CH.sub.2 OCH.sub.2 CH.sub.2                                                                   CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                            1                                    461        CH.sub.2 OCH.sub.2 CH.sub.2                                                                   CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                            2                                    462        CH.sub.2 OCH.sub.2 CH.sub.2                                                                   CH.sub.2 CH.sub.2 OSO.sub.3 H                                                               0                                    463        CH.sub.2 OCH.sub.2 CH.sub.2                                                                   CH.sub.2 CH.sub.2 OSO.sub.3 H                                                               1                                    ______________________________________                                    

EXAMPLE 464

32 g of the compound of the formula ##STR438## described in Example 350were added at 0°-10° C. to 120 g of chlorosulfonic acid and the mixturewas stirred at 20°-25° C. for 2 hours. Discharging the mixture onto 300g of ice-water left the product of the formula ##STR439## in solution.If the sulfuric ester was used for diazotization reactions, thediazotization was carried out from a sulfuric acid solution. Forcondensation with heterocyclic attachment components, the sulfuric acidsolution was neutralized with sodium bicarbonate and further reacted asa solution.

The same method can be used to obtain the following compounds of thegeneral formula: ##STR440##

                  TABLE 20                                                        ______________________________________                                        Ex. No.                                                                              R.sup.1         R.sup.2         n                                      ______________________________________                                        465    CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                 CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                 0                                      466    CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                 CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                 1                                      467    CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                 CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              0                                      468    CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                 CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              1                                      469    CH.sub.2 CH.sub.2 OSO.sub.3 H                                                                 CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              2                                      470    CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              0                                      471    CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              1                                      472    CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              2                                      473    CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              CH.sub.3 CH.sub.2 OSO.sub.3 H                                                                 0                                      474    CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              CH.sub.3 CH.sub.2 OSO.sub.3 H                                                                 1                                      475    CH.sub.2 CH(CH.sub.3)OSO.sub.3 H                                                              CH.sub.3 CH.sub.2 OSO.sub.3 H                                                                 2                                      ______________________________________                                    

We claim:
 1. A double attachment reactive dye of the formula (I): ##STR441## wherein U¹ is C₁ -C₄ -alkyl, phenyl, C₂ -C₁₀ -alkenyl or a radical of the formula: ##STR442## wherein Q¹ and Q² are identical or different and each is independently of the other hydrogen or C₁ -C₄ -alkyl, and Q³ is a group which is detachable under alkaline reaction conditions,Z is the radical of the formula: ##STR443## wherein Q⁴ is, independently of the other, hydrogen or C₁ -C₄ -alkyl which is unsubstituted or substituted by cyano; U² is C₁ -C₄ -alkyl, phenyl, C₂ -C₁₀ -alkenyl or a radical of the formula: ##STR444## wherein Q⁵ and Q⁶ are identical or different and each is, independently of the other, hydrogen or C₁ -C₄ -alkyl, and Q⁷ is a group which is detachable under alkaline reaction conditions, and w is 2, t is 2, v is 1 or 2, X is a) a radical of a chromophore which either does not have a further reactive group or which does have a further reactive group, and which is derived from a mono- or disazo dye or a copper formazan, or b) a radical of a coupling component which additionally may be linked to the radical of a diazo component via an azo bridge and which may additionally have a reactive group, and L is a) a bridge member of the formula: ##STR445## wherein Q⁸ is hydrogen or C₁ -C₄ -alkyl, Q⁹ and Q¹⁰ are identical or different and each is independently of the other hydrogen or C₁ -C₄ -alkyl, and Q¹¹ is fluorine, chlorine or bromine; or b) an azo bridge, with the proviso that at least one of the two radicals U¹ and U² is not C₁ -C₄ -alkyl or phenyl.
 2. The double attachment reactive dye as claimed in claim 1, of the formula (Ia):

    X[--L--E.sup.1 ].sub.v                                     (Ia)

wherein X, L and v are each as defined in claim 1, and E¹ is a radical of the formula (IIa): ##STR446## wherein Q² is hydrogen or methyl, Q³ is OSO₃ H, Z is the radical of the formula: ##STR447## wherein Q⁶ is hydrogen or methyl.
 3. The double attachment reactive dye as claimed in claim 1, of the formula (Ib):

    X[--L--E.sup.2 ].sub.v

wherein X, L and v are each as defined above and E² is a radical of the formula (IIb): ##STR448## wherein Q² and Q⁶ are each, independently of the other, hydrogen or methyl.
 4. The double attachment reactive dye as claimed in claim 1, of the formula (Ic):

    X[--L--]E.sup.3 ].sub.v

wherein X, L and v are each as defined above and E³ is a radical of the formula (IIc): ##STR449## 